Aromatic compound, organic semiconductor layer, and organic thin film transistor

Abstract

The purpose of the present invention is to provide: an aromatic compound having a specific substituent, said aromatic compound being a coating-type organic semiconductor material that has high carrier mobility, high heat resistance and adequate solubility; an organic semiconductor layer which uses this aromatic compound; and an organic thin film transistor.　The purpose is achieved by an aromatic compound which is represented by formula (1-I) or (1-II). In formulae (1-I) and (1-II), Ar represents a monocyclic ring or the like; each of X1 and X2 represents an oxygen atom or the like; each of Y1 and Y2 represents CR6 or the like; each of R1 to R6 represents a hydrogen atom or the like; and at least one of the R1 to R6 moieties is a group that is represented by formula (2). In formula (2), A represents a specific alkenyl group or the like; each of l and n represents 0 or 1; m represents an integer from 1 to 20; and each of Z1 and Z2 represents a hydrogen atom or the like.

Description

[Technical Field]

[0001] The present invention relates to novel aromatic compounds that can be applied to electronic materials such as organic semiconductor materials, organic semiconductor layers using the same, and organic thin-film transistors. In particular, the present invention relates to aromatic compounds having specific substituents that have excellent solubility and heat resistance and are therefore applicable to various device fabrication processes, and organic semiconductor layers and organic thin-film transistors using the same. [Background technology]

[0002] Organic semiconductor devices, typified by organic thin-film transistors, have attracted attention in recent years because they offer features not found in inorganic semiconductor devices, such as energy conservation, low cost, and flexibility. These organic semiconductor devices are composed of several materials, including an organic semiconductor layer, a substrate, an insulating layer, and electrodes. Among these, the organic semiconductor layer, which is responsible for the transport of charge carriers, plays a central role in the device. Since the performance of organic semiconductor devices depends on the carrier mobility of the organic semiconductor material that constitutes this organic semiconductor layer, the development of organic semiconductor materials that provide high carrier mobility is desired. Commonly known methods for producing organic semiconductor layers include vacuum deposition, in which organic materials are vaporized under high temperature and vacuum, and coating, in which organic materials are dissolved in a suitable solvent and the resulting solution is coated. Of these, the coating method can be carried out using printing technology without using high temperature and high vacuum conditions, and is therefore expected to significantly reduce the manufacturing costs of device fabrication, making it an economically preferable process. From the viewpoint of high carrier mobility and device fabrication process, the organic semiconductor material used in such coating methods preferably has heat resistance of 130°C or higher and a solubility of 0.1% by weight or higher at room temperature. Furthermore, in the case of transistors used for electronic paper or organic EL applications, the carrier mobility should be 1.0 cm. 2 / V·sec or more is preferable.

[0003] Small molecule semiconductors with rod-shaped molecular axes based on fused ring systems are generally known to exhibit high carrier mobility due to their higher crystallinity compared to polymer semiconductors. However, small molecule semiconductors generally suffer from low solubility. While semiconductors incorporating alkyl groups to improve solubility have been reported, these have encountered problems with reduced carrier mobility and heat resistance. Semiconductors incorporating aromatic substituents to achieve high carrier mobility through π-stacking have also been reported, but these have been reported to exhibit significantly reduced solubility in exchange for high mobility. Therefore, few small molecule organic semiconductor materials are known that combine high carrier mobility, high heat resistance, and adequate solubility. Currently, proposed low molecular weight materials include 2,7-dialkyl-substituted benzothienobenzothiophenes (see, for example, Patent Document 1 and Non-Patent Document 1), 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophenes (see, for example, Non-Patent Document 2), and dithienobiphenylene derivatives (see, for example, Patent Document 2). However, the dialkyl-substituted benzothienobenzothiophenes described in Patent Document 1 and Non-Patent Document 1 have a problem with heat resistance, in that transistor operation is lost when heated to 130° C. or higher.

[0004] 2,7-Diphenyl[1]benzothieno[3,2-b][1]benzothiophene described in Non-Patent Document 2 generally has little solubility in organic solvents, and therefore has a problem with solubility.

[0005] Furthermore, the alkyl-substituted dithienobiphenylene derivative described in Patent Document 2 has both high heat resistance and moderate solubility and can be suitably used in organic semiconductors, but compounds having even higher carrier mobility have been desired. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2008 / 047896 publication [Patent Document 2] JP 2018 / 174322 A [Non-patent literature]

[0007] [Non-Patent Document 1] Journal of the American Chemical Society, 2007, vol. 129, pp. 15732-15733 [Non-patent document 2] Journal of the American Chemical Society, 2006, vol. 128, pp. 12604-12605 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel coating-type organic semiconductor material that has high carrier mobility, high heat resistance, and appropriate solubility. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the present inventors have found that novel aromatic compounds having specific substituents can be used as organic semiconductor materials that not only provide high carrier mobility but also have high heat resistance and appropriate solubility, and have thus completed the present invention.

[0010] That is, the present invention relates to an aromatic compound represented by either formula (1-I) or formula (1-II) below, an organic semiconductor layer containing the aromatic compound, and an organic thin-film transistor including the semiconductor layer. [ka] [(wherein Ar represents a single ring or 2 to 6 condensed rings. X 1 , X 2 are each independently an oxygen atom, a sulfur atom, a selenium atom, or NR 3 , or CR 4 =CR 5 Y represents one of the group consisting of 1 , Y2 are each independently 6 or nitrogen atom. 1 ~R 6 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the following formula (2), and R 1 ~R 6 At least one of the groups is a group represented by the following formula (2): [ka] (wherein A represents one of the group consisting of an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 4 to 26 carbon atoms; l and n each independently represent 0 or 1; m represents an integer of 1 to 20. Z 1 , Z 2 and each occurrence may be the same or different and represent one of the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms.) [Effects of the Invention]

[0011] The novel aromatic compounds of the present invention provide high carrier mobility, as well as high heat resistance and suitable solubility, and therefore can provide organic thin-film transistors that exhibit excellent semiconductor properties through coating, which is extremely effective. [Brief explanation of the drawings]

[0012] [Figure 1] 1A and 1B are diagrams illustrating the cross-sectional structure of an organic thin film transistor. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below.

[0014] The present invention is an aromatic compound represented by either formula (1-I) or formula (1-II) above (hereinafter referred to as "the compound of the present invention").

[0015] In formula (1-I) and formula (1-II), Ar represents a single ring or 2 to 6 fused rings. To exhibit higher carrier mobility, Ar preferably represents 2 to 4 fused rings, and to exhibit higher solubility, Ar more preferably represents 2 to 3 fused rings. Each of the rings constituting the single ring or the 2 to 6 fused rings is a 4 to 8 membered ring, and a 4 to 6 membered ring is preferred because this facilitates π-stacking. Specific examples of the monocyclic ring or 2 to 6 fused rings represented by Ar include monocyclic rings such as a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, an oxazole ring, a pyrrole ring, an imidazole ring, a benzene ring, and a pyridine ring, and fused rings such as a thienothiophene ring, a naphthalene ring, a biphenylene ring, an anthracene ring, a dithienothiophene ring, a dithienobenzo ring, a benzothienobenzothiophene ring, a tetracene ring, a bis(dithieno)benzo ring, and a bis(benzothieno)benzo ring. In order to exhibit higher carrier mobility, fused rings of 2 to 4 rings such as a thienothiophene ring, a naphthalene ring, a biphenylene ring, an anthracene ring, a dithienothiophene ring, and a benzothienobenzothiophene ring are preferred, and fused rings of 2 to 3 rings such as a thienothiophene ring, a naphthalene ring, a biphenylene ring, and an anthracene ring are more preferred.

[0016] X in formula (1-I) and formula (1-II) 1 , X 2 are each independently an oxygen atom, a sulfur atom, a selenium atom, or NR 3 , or CR 4 =CR 5 In order for the compound of the present invention to exhibit higher stability, X 1 and X 2 At least one of the following is a sulfur atom or CR 4 =CR 5 Preferably, it is any one of the following, and more preferably a sulfur atom. Y in formula (1-I) and formula (1-II) 1 , Y 2 are each independently 6 or a nitrogen atom. In order for the compound of the present invention to exhibit higher stability, Y 1 and Y 2 At least one of the following is CR 6 It is preferable that:

[0017] R in formula (1-I) and formula (1-II) 1 ~R 6 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 1 ~R 6 At least one of the groups is a group represented by formula (2). The R 1 ~R 6 The halogen atom in represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom because it is stable.

[0018] The R 1 ~R 6Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isovaleryl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, alkyl groups having 1 to 14 carbon atoms are preferred, as they result in aromatic compounds that exhibit particularly high carrier mobility and high solubility, and linear alkyl groups having 1 to 14 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups, are more preferred. The R 1 ~R 6 Examples of the alkenyl group having 2 to 20 carbon atoms in the formula (I) include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups. The R 1 ~R 6 Examples of the alkynyl group having 2 to 20 carbon atoms in the formula (I) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, and an n-dodecynyl group.

[0019] The R 1 ~R 6Examples of the alkadienyl group having 4 to 22 carbon atoms in the formula (I) include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonadienyl group, an n-decadienyl group, an n-dodecadienyl group, and an n-tridecadienyl group. An alk-1,3-dienyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-dienyl group, an n-hepta-1,3-dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, or an n-deca-1,3-dienyl group is more preferred. The R 1 ~R 6 Examples of the alkadiynyl group having 4 to 22 carbon atoms in the formula (I) include a butadiynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadiynyl group, an n-octadiynyl group, an n-nonadiynyl group, an n-decadiynyl group, an n-dodecadiynyl group, an n-tridecadiynyl group, and the like. A 1,3-alkadiynyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-diynyl group, an n-hepta-1,3-diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, or an n-deca-1,3-diynyl group is more preferred. The R 1 ~R 6The aryl group having 4 to 26 carbon atoms in the formula (I) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; alkyl-substituted phenyl groups such as a p-tolyl group, a p-(n-hexyl)phenyl group, a p-(n-octyl)phenyl group, and a p-(2-ethylhexyl)phenyl group; a 2-furyl group; a 2-thienyl group; a 5-fluoro-2-furyl group, a 5-methyl-2-furyl group, a 5-ethyl-2-furyl group, a 5-(n-propyl)-2-furyl group, a 5-(n-butyl)-2-furyl group, a 5-(n-pentyl)-2-furyl group, and a 5-(n-hexyl)-2-furyl group. , a 5-(n-octyl)-2-furyl group, a 5-(2-ethylhexyl)-2-furyl group, a 5-fluoro-2-thienyl group, a 5-methyl-2-thienyl group, a 5-ethyl-2-thienyl group, a 5-(n-propyl)-2-thienyl group, a 5-(n-butyl)-2-thienyl group, a 5-(n-pentyl)-2-thienyl group, a 5-(n-hexyl)-2-thienyl group, a 5-(n-octyl)-2-thienyl group, and a 5-(2-ethylhexyl)-2-thienyl group.

[0020] These R 1 ~R 6 Among these, from the viewpoint of stability, R is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or one of the group represented by formula (2), and from the viewpoint of high solubility, R is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (2), and from the viewpoint of high carrier mobility, R 1 and R 2 Only one or both of R represents a group represented by formula (2), 3 ~R 6 It is more preferable that is a hydrogen atom.

[0021] In formula (2), A represents one of the group consisting of an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 4 to 26 carbon atoms, and an aryl group having 4 to 26 carbon atoms is more preferred because it exhibits higher carrier mobility. Examples of the alkenyl group having 2 to 20 carbon atoms in formula (2) include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-group, cyclohexenyl-1-group, cycloheptenyl-1-group, 2-phenylethenyl, 1-phenylethenyl, 2-(4-methylphenyl)ethenyl, and 2-(4-n-butyl)ethenyl. Examples of the alkynyl group having 2 to 20 carbon atoms in the formula (2) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, an n-dodecynyl group, a 2-phenylethynyl group, a 1-phenylethynyl group, a 2-(4-methylphenyl)ethynyl group, and a 2-(4-n-butyl)ethynyl group.

[0022] The aryl group having 4 to 26 carbon atoms in the formula (2) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group, a p-tolyl group, a p-ethylphenyl group, a p-(n-propyl)phenyl group, a p-(isopropyl)phenyl group, a p-(n-butyl)phenyl group, a p-(2-methylpropyl)phenyl group, a p-(n-pentyl)phenyl group, a p-(3-methylbutyl)phenyl group, a p-(n-hexyl)phenyl group, a p-(4-methylpentyl)phenyl group, and a p-(n-heptyl)phenyl group. alkyl-substituted phenyl groups such as p-(n-octyl)phenyl, p-(2-ethylhexyl)phenyl, m-ethylphenyl, m-(n-propyl)phenyl, m-(n-butyl)phenyl, m-(2-methylpropyl)phenyl, o-ethylphenyl, o-(n-propyl)phenyl, and indanyl-5-yl; p-methoxyphenyl, p-ethoxyphenyl, p-(n-propyloxy)phenyl, and p-(n- alkyloxy-substituted phenyl groups such as p-(n-butylphenyloxy)phenyl group, p-(n-pentyloxy)phenyl group, p-(n-hexyloxy)phenyl group, p-(n-heptyloxy)phenyl group, p-(n-octyloxy)phenyl group, m-methoxyphenyl group, m-(n-propyloxy)phenyl group, o-methoxyphenyl group, o-(n-propyloxy)phenyl group, 3,4-methylenedioxyphenyl group, 3,4-ethylenedioxyphenyl group, 2,3-dihydrobenzofuran-5-yl, and 2,3-dihydrobenzofuran-6-yl; fluorine-substituted phenyl groups such as p-fluorophenyl group, m-fluorophenyl group, o-fluorophenyl group, 3,5-difluorophenyl group, perfluorophenyl group, p-(trifluoromethyl)phenyl group, m-(trifluoromethyl)phenyl group, and o-(trifluoromethyl)phenyl group; 2-furyl group, 2-thienyl group;5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5-(n-propyl)-2-furyl group, 5-(n-butyl)-2-furyl group, 5-(n-pentyl)-2-furyl group, 5-(n-hexyl)-2-furyl group, 5-(n-octyl)-2-furyl group, 5-(2-ethylhexyl)-2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-(n-propyl)-2-thienyl group, 5-(n-butyl)-2-furyl group Examples of alkyl-substituted heteroaryl groups include 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl, 5-(2-ethylhexyl)-2-thienyl, thieno[3,2-b]thiophen-2-yl, 5-methylthieno[3,2-b]thiophen-2-yl, 5-ethylthieno[3,2-b]thiophen-2-yl, and 5-(n-butyl)thieno[3,2-b]thiophen-2-yl. Among these, phenyl and alkyl-substituted phenyl groups are more preferred because they exhibit particularly high carrier mobility and high solubility.

[0023] In formula (2), l and n each independently represent 0 or 1, and n is preferably 0 for ease of synthesis, and more preferably both l and n are 0 for high carrier mobility. In formula (2), m represents an integer of 1 to 20, and is preferably an integer of 1 to 8 for high solubility, more preferably an integer of 1 to 4, and even more preferably 2 for high carrier mobility.

[0024] Z in equation (2) 1 , Z 2 and each occurrence may be the same or different and represent one of the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms. The Z 1 , Z 2 The halogen atom in represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom because it is stable. The Z 1 , Z2 Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isovaleryl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, alkyl groups having 1 to 8 carbon atoms are preferred, and methyl, ethyl, and n-propyl are more preferred, as they result in aromatic compounds that exhibit particularly high carrier mobility and high solubility. The Z 1 , Z 2 is preferably either a hydrogen atom or a halogen atom due to high carrier mobility, and more preferably a hydrogen atom. In formula (2), A is either a phenyl group or an alkyl-substituted phenyl group, l and n are both 0, m is an integer of 1 to 4, and Z 1 , Z 2 is preferably either a hydrogen atom or a halogen atom, which allows the compound of the present invention to exhibit higher carrier mobility. The group represented by formula (2) is preferably a 2-phenylethyl group or a 2-alkyl-substituted phenylethyl group for high carrier mobility, and is preferably a 2-phenylethyl group, a 2-(4-methylphenyl)ethyl group, a 2-(4-ethylphenyl)ethyl group, a 2-(4-n-propylphenyl)ethyl group, a 2-(4-n-butylphenyl)ethyl group, a 2-(4-n-pentylphenyl)ethyl group, a 2-(4-n-hexylphenyl)ethyl group, a 2-(4-n-

[0047] A 2-(4-n-heptylphenyl)ethyl group, a 2-(4-n-octylphenyl)ethyl group, a 2-(4-n-nonylphenyl)ethyl group, or a 2-(4-n-decylphenyl)ethyl group is more preferred, and a 2-phenylethyl group, a 2-(4-n-propylphenyl)ethyl group, a 2-(4-n-butylphenyl)ethyl group, a 2-(4-n-pentylphenyl)ethyl group, a 2-(4-n-hexylphenyl)ethyl group, or a 2-(4-n-heptylphenyl)ethyl group is even more preferred.

[0025] The aromatic compound of formula (1-I) or formula (1-II) is preferably an aromatic compound represented by one of the group consisting of the following formulae (3-1) to (3-6) in view of ease of synthesis. [ka] [(where X 3 , X 4 , X 5 are independently an oxygen atom, a sulfur atom, a selenium atom, a single bond, or NR 17 , or CR 18 =CR 19 R represents one of the groups consisting of 7 ~R 10 Among the combinations of two adjacent pairs of R, only one pair constitutes the following formula (4), and R 11 ~R 14 Among the combinations of adjacent two of these, only one pair constitutes the following formula (4-2), forming a 5- or 6-membered ring, respectively. 7 ~R 14 , and R 15 ~R 19each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2). [ka] (where X 6 are oxygen atoms, sulfur atoms, selenium atoms, CR 21 =CR 22 , or NR 23 Y represents one of the group consisting of 3 is CR 24 or nitrogen atom. 21 ~R 24 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2), and R 20 is a group represented by the formula (2). [ka] (where X 6 , Y 3 , R 21 ~R 24 is X in the formula (4) 6 , Y 3 , R 21 ~R 24 and R 20b represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2).

[0026] In formulas (3-1) to (3-6), R 7 ~R 10Of the combinations of adjacent two of these, only one pair constitutes the above formula (4), and R 11 ~R 14 Of the combinations of adjacent two of these, only one pair constitutes the above formula (4-2), forming a 5- or 6-membered ring, respectively. R that did not constitute formula (4) and formula (4-2) 7 ~R 14 , R 15 ~R 19 , R in formula (4) and formula (4-2) 21 ~R 24 each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2). R 20 is a group represented by formula (2). R 20b is a group represented by one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and is preferably a hydrogen atom, a fluorine atom, or a group represented by formula (2) because it has high mobility.

[0027] In the compound represented by one of the group consisting of formulas (3-1) to (3-6), formula (4-2) is preferably the following formula (4-3). [ka] (where X 6 , Y 3 , R 21 ~R 24 is X in the formula (4) 6 , Y 3 , R 21 ~R 24 and R 20crepresents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms.

[0028] R 20c is one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms, and is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom, because they have high mobility.

[0029] In the compound represented by one of the group consisting of formulas (3-1) to (3-6), formula (4-2) is also preferably the following formula (4-4). [ka] (where X 6 , Y 3 , R 21 ~R 24 is X in the formula (4) 6 , Y 3 , R 21 ~R 24 and R 20d is a group represented by the formula (2).

[0030] The definition of the group represented by formula (2) in formulas (3-1) to (3-6) is the same as the definition of formula (2) in the above-mentioned formulas (1-I) and (1-II).

[0031] The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20cThe halogen atom in represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom because it is stable. The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isovaleryl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, alkyl groups having 1 to 14 carbon atoms are preferred, as they result in aromatic compounds that exhibit particularly high carrier mobility and high solubility, and linear alkyl groups having 1 to 14 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups, are more preferred. The R 7 ~R 24 Examples of the alkenyl group having 2 to 20 carbon atoms in the formula (I) include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups. The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20cExamples of the alkynyl group having 2 to 20 carbon atoms in the formula (I) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, and an n-dodecynyl group.

[0032] The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c Examples of the alkadienyl group having 4 to 22 carbon atoms in the formula (I) include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonadienyl group, an n-decadienyl group, an n-dodecadienyl group, and an n-tridecadienyl group. An alk-1,3-dienyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-dienyl group, an n-hepta-1,3-dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, or an n-deca-1,3-dienyl group is more preferred. The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c Examples of the alkadiynyl group having 4 to 22 carbon atoms in the formula (I) include a butadiynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadiynyl group, an n-octadiynyl group, an n-nonadiynyl group, an n-decadiynyl group, an n-dodecadiynyl group, an n-tridecadiynyl group, and the like. A 1,3-alkadiynyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-diynyl group, an n-hepta-1,3-diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, or an n-deca-1,3-diynyl group is more preferred. The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20cThe aryl group having 4 to 26 carbon atoms in the formula (I) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; alkyl-substituted phenyl groups such as a p-tolyl group, a p-(n-hexyl)phenyl group, a p-(n-octyl)phenyl group, and a p-(2-ethylhexyl)phenyl group; a 2-furyl group; a 2-thienyl group; a 5-fluoro-2-furyl group, a 5-methyl-2-furyl group, a 5-ethyl-2-furyl group, a 5-(n-propyl)-2-furyl group, a 5-(n-butyl)-2-furyl group, a 5-(n-pentyl)-2-furyl group, and a 5-(n-hexyl)-2-furyl group. , a 5-(n-octyl)-2-furyl group, a 5-(2-ethylhexyl)-2-furyl group, a 5-fluoro-2-thienyl group, a 5-methyl-2-thienyl group, a 5-ethyl-2-thienyl group, a 5-(n-propyl)-2-thienyl group, a 5-(n-butyl)-2-thienyl group, a 5-(n-pentyl)-2-thienyl group, a 5-(n-hexyl)-2-thienyl group, a 5-(n-octyl)-2-thienyl group, and a 5-(2-ethylhexyl)-2-thienyl group.

[0033] The R 7 ~R 19 is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or one member of the group represented by formula (2) for stability, and more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms for high solubility. The R 21 ~R 24 is preferably one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2) for stability, and R 21 ~R 24 is more preferably selected from the group consisting of a hydrogen atom and a methyl group, and even more preferably a hydrogen atom.

[0034] X in formulas (3-1) to (3-6) 3, X 4 , X 5 is an oxygen atom, a sulfur atom, a selenium atom, a single bond, NR 17 , or CR 18 =CR 19 and represents one of the group consisting of sulfur atoms, single bonds, or CR 18 =CR 19 Preferably, either a sulfur atom or CR 18 =CR 19 is more preferred, and a sulfur atom is even more preferred. X in formulas (4) and (4-2) to (4-3) 6 is an oxygen atom, a sulfur atom, a selenium atom, a CR 21 =CR 22 , or NR 23 Sulfur atoms or CR due to high carrier mobility. 21 =CR 22 is preferred, and a sulfur atom is more preferred. Y in formulas (4) and (4-2) to (4-3) 3 is CR 24 or nitrogen atom, and for stability, CR 24 is preferred.

[0035] The aromatic compounds represented by formulas (3-1) to (3-6) preferably have a point-symmetric or axisymmetric structure, and more preferably a point-symmetric structure, due to their high carrier mobility. Of the aromatic compounds represented by formulas (3-1) to (3-6), formula (3-1) or formula (3-2) is preferred due to its high solubility and high heat resistance.

[0036] The aromatic compound represented by formula (1-I) or formula (1-II) is preferably an aromatic compound represented by the following formula (5) or formula (5-2). [ka] [(where R 25 ~R 28 Among the combinations of adjacent two of these, only one pair constitutes the following formula (6), and R 29 ~R 32Among the combinations of adjacent two of these, only one pair constitutes the following formula (6-2), forming a 5- or 6-membered ring, respectively. 25 ~R 32 and R 69 , R 70 each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2). [ka] (where X 7 are oxygen atoms, sulfur atoms, selenium atoms, CR 34 =CR 35 , or NR 36 Y 4 is CR 37 or nitrogen atom. 34 ~R 37 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2), and R 33 is a group represented by the formula (2). [ka] (where X 7 , Y 4 , R 34 ~R 37 is X in the formula (6) 7 , Y 4 , R 34 ~R 37 and R 33brepresents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2).

[0037] In formulas (5) and (5-2), R 25 ~R 28 Of the combinations of adjacent two of these, only one pair constitutes the above formula (6), and R 29 ~R 32 Of the combinations of adjacent two of these, only one pair constitutes the above formula (6-2), forming a 5- or 6-membered ring, respectively. R that did not constitute formula (6) and formula (6-2) 25 ~R 32 and R 69 , R 70 , R in Equation (6) and Equation (6-2) 34 ~R 37 each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2). R 33 is a group represented by formula (2). R 33b is a group represented by one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and is preferably a hydrogen atom, a fluorine atom, or a group represented by formula (2) because it has high mobility.

[0038] In the aromatic compound represented by formula (5) or formula (5-2), formula (6-2) is preferably the following formula (6-3). [ka] (where X 7 , Y 4 , R 34 ~R 37 is X in the formula (6) 7 , Y 4 , R 34 ~R 37 and R 33c represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms.

[0039] R 33c is one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms, and is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom, because they have high mobility.

[0040] In the aromatic compound represented by formula (5) or formula (5-2), formula (6-2) is also preferably the following formula (6-4). [ka] (where X 7 , Y 4 , R 34 ~R 37 is X in the formula (6) 7 , Y 4 , R 34 ~R 37 and R 33d is a group represented by the formula (2).

[0041] The definition of the group represented by formula (2) in formula (5) and formula (5-2) is the same as the definition of formula (2) in formula (1-I) and formula (1-II) above.

[0042] The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The halogen atom in represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom because it is stable. The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isovaleryl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, alkyl groups having 1 to 14 carbon atoms are preferred, as they result in aromatic compounds that exhibit particularly high carrier mobility and high solubility, and linear alkyl groups having 1 to 14 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups, are more preferred. The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33cExamples of the alkenyl group having 2 to 20 carbon atoms in the formula (I) include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups. The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c Examples of the alkynyl group having 2 to 20 carbon atoms in the formula (I) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, and an n-dodecynyl group.

[0043] The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c Examples of the alkadienyl group having 4 to 22 carbon atoms in the formula (I) include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonadienyl group, an n-decadienyl group, an n-dodecadienyl group, and an n-tridecadienyl group. An alk-1,3-dienyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-dienyl group, an n-hepta-1,3-dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, or an n-deca-1,3-dienyl group is more preferred. The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33cExamples of the alkadiynyl group having 4 to 22 carbon atoms in the formula (I) include a butadiynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadiynyl group, an n-octadiynyl group, an n-nonadiynyl group, an n-decadiynyl group, an n-dodecadiynyl group, an n-tridecadiynyl group, and the like. A 1,3-alkadiynyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-diynyl group, an n-hepta-1,3-diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, or an n-deca-1,3-diynyl group is more preferred. The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The aryl group having 4 to 26 carbon atoms in the formula (I) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; alkyl-substituted phenyl groups such as a p-tolyl group, a p-(n-hexyl)phenyl group, a p-(n-octyl)phenyl group, and a p-(2-ethylhexyl)phenyl group; a 2-furyl group; a 2-thienyl group; a 5-fluoro-2-furyl group, a 5-methyl-2-furyl group, a 5-ethyl-2-furyl group, a 5-(n-propyl)-2-furyl group, a 5-(n-butyl)-2-furyl group, a 5-(n-pentyl)-2-furyl group, and a 5-(n-hexyl)-2-furyl group. , a 5-(n-octyl)-2-furyl group, a 5-(2-ethylhexyl)-2-furyl group, a 5-fluoro-2-thienyl group, a 5-methyl-2-thienyl group, a 5-ethyl-2-thienyl group, a 5-(n-propyl)-2-thienyl group, a 5-(n-butyl)-2-thienyl group, a 5-(n-pentyl)-2-thienyl group, a 5-(n-hexyl)-2-thienyl group, a 5-(n-octyl)-2-thienyl group, and a 5-(2-ethylhexyl)-2-thienyl group.

[0044] The R 25 ~R 32 , R 69 , R 70is preferably one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2) for stability, and is more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms for high solubility, and is further preferably selected from the group consisting of a hydrogen atom or a methyl group. The R 34 ~R 37 is preferably one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2) in terms of stability, and is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (2) in terms of high carrier mobility, and R 34 ~R 37 It is even more preferred that is a hydrogen atom.

[0045] X in formulas (6) and (6-2) to (6-4) 7 is an oxygen atom, a sulfur atom, a selenium atom, a CR 34 =CR 35 , or NR 36 In view of high solubility, sulfur atom, oxygen atom, sulfur atom and selenium atom are preferred, and sulfur atom is more preferred due to high carrier mobility. Y in equations (6) and (6-2) to (6-4) 4 is CR 37 or nitrogen atom, and CR for stability 37 is preferred.

[0046] The aromatic compounds represented by formula (5) and formula (5-2) preferably have a point-symmetric or axially symmetric structure, and more preferably a point-symmetric structure, due to their high carrier mobility. Of the aromatic compounds represented by formula (5) and formula (5-2), formula (5) is preferred due to its high solubility.

[0047] Furthermore, the aromatic compound represented by formula (5) or formula (5-2) is preferably one kind of compound selected from the group consisting of the following formulae (7-1) to (7-5) in terms of ease of synthesis. [ka] (where X 8 , X 9 are each independently an oxygen atom, a sulfur atom, a selenium atom, or NR 44 Y represents one of the group consisting of 5 , Y 6 are each independently 45 or nitrogen atom. 38 ~R 45 , R 71 , R 72 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 38 ~R 45 at least one of R is a group represented by formula (2), 38 and R 41 At least one of the groups is a group represented by formula (2).

[0048] X in equations (7-1) to (7-5) 8 , X 9 are each independently an oxygen atom, a sulfur atom, a selenium atom, or NR 44 In view of stability, a sulfur atom, an oxygen atom, a sulfur atom, or a selenium atom is preferred, and a sulfur atom is more preferred due to high carrier mobility. Y in equations (7-1) to (7-5) 5 , Y 6 are each independently 45 or nitrogen atom, and for stability, CR 45 is preferred.

[0049] R in equations (7-1) to (7-5) 38 ~R 45 , R 71 , R 72each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the above formula (2), and R 38 ~R 45 At least one of these is a group represented by the above formula (2). R in equations (7-1) to (7-5) 38 , R 41 Either one or both of are a group represented by formula (2). The definition of the group represented by formula (2) in formulas (7-1) to (7-5) is the same as the definition of formula (2) in the above-mentioned formulas (1-I) and (1-II).

[0050] The R 38 ~R 45 , R 71 , R 72 The halogen atom in represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom because it is stable. The R 38 ~R 45 , R 71 , R 72Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isovaleryl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, alkyl groups having 1 to 14 carbon atoms are preferred, as they result in aromatic compounds that exhibit particularly high carrier mobility and high solubility, and linear alkyl groups having 1 to 14 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups, are more preferred. The R 38 ~R 45 , R 71 , R 72 Examples of the alkenyl group having 2 to 20 carbon atoms in the formula (I) include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups. The R 38 ~R 45 , R 71 , R 72 Examples of the alkynyl group having 2 to 20 carbon atoms in the formula (I) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, and an n-dodecynyl group.

[0051] The R 38 ~R 45 , R71 , R 72 Examples of the alkadienyl group having 4 to 22 carbon atoms in the formula (I) include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonadienyl group, an n-decadienyl group, an n-dodecadienyl group, and an n-tridecadienyl group. An alk-1,3-dienyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-dienyl group, an n-hepta-1,3-dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, or an n-deca-1,3-dienyl group is more preferred. The R 38 ~R 45 , R 71 , R 72 Examples of the alkadiynyl group having 4 to 22 carbon atoms in the formula (I) include a butadiynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadiynyl group, an n-octadiynyl group, an n-nonadiynyl group, an n-decadiynyl group, an n-dodecadiynyl group, an n-tridecadiynyl group, and the like. A 1,3-alkadiynyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-diynyl group, an n-hepta-1,3-diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, or an n-deca-1,3-diynyl group is more preferred. The R 38 ~R 45 , R 71 , R 72The aryl group having 4 to 26 carbon atoms in the formula (I) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; alkyl-substituted phenyl groups such as a p-tolyl group, a p-(n-hexyl)phenyl group, a p-(n-octyl)phenyl group, and a p-(2-ethylhexyl)phenyl group; a 2-furyl group; a 2-thienyl group; a 5-fluoro-2-furyl group, a 5-methyl-2-furyl group, a 5-ethyl-2-furyl group, a 5-(n-propyl)-2-furyl group, a 5-(n-butyl)-2-furyl group, a 5-(n-pentyl)-2-furyl group, and a 5-(n-hexyl)-2-furyl group. , a 5-(n-octyl)-2-furyl group, a 5-(2-ethylhexyl)-2-furyl group, a 5-fluoro-2-thienyl group, a 5-methyl-2-thienyl group, a 5-ethyl-2-thienyl group, a 5-(n-propyl)-2-thienyl group, a 5-(n-butyl)-2-thienyl group, a 5-(n-pentyl)-2-thienyl group, a 5-(n-hexyl)-2-thienyl group, a 5-(n-octyl)-2-thienyl group, and a 5-(2-ethylhexyl)-2-thienyl group.

[0052] The R 38 ~R 45 , R 71 , R 72 From the viewpoint of stability, R is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and from the viewpoint of high solubility, R is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (2). 38 , R 41 is preferably one of the group consisting of the group represented by the above formula (2), a hydrogen atom, and a fluorine atom, and more preferably one of the group consisting of the group represented by the above formula (2) and a hydrogen atom, and R 38 and R 41 It is more preferable that both of R and R are groups represented by the above formula (2). 39 , R 40 , R 42 ~R 45 , R 71 , R72 It is even more preferred that is selected from the group consisting of a hydrogen atom and a methyl group, with a hydrogen atom being even more preferred.

[0053] The aromatic compounds represented by the above formulas (7-1) to (7-5) preferably have a point-symmetric or axisymmetric structure, and more preferably a point-symmetric structure, due to their high carrier mobility.

[0054] Of the formulas (7-1) to (7-5), any of formulas (7-1), (7-2) and (7-5) is preferred for high solubility, and formula (7-1) is more preferred for high carrier mobility.

[0055] More preferred compound structures of the compound of the present invention are represented by one of the group consisting of the following formulae (8-1) to (8-11) in addition to the above formulae (7-1) to (7-5). Among these, from the viewpoints of high heat resistance and high solubility, aromatic compounds having 4 to 5 condensed rings and selected from the group consisting of formulae (7-1) to (7-5) and (8-2) to (8-9) are preferred, and from the viewpoint of high carrier mobility, aromatic compounds having a point-symmetric structure and selected from the group consisting of formulae (7-1) to (7-5), (8-2) to (8-3), and (8-5) to (8-8) are even more preferred. [ka] (where X is an oxygen atom, a sulfur atom, a selenium atom, or NR 58 , or CR 59 =CR 60 Y represents one of the groups consisting of CR 61 or nitrogen atom. 46 ~R 61 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 46 ~R 61 at least one of R is a group represented by formula (2), 46 and R47 At least one of the groups is a group represented by formula (2), and o represents 0 or 1.

[0056] X in formulas (8-1) to (8-11) is an oxygen atom, a sulfur atom, a selenium atom, or NR 58 , or CR 59 =CR 60 In view of stability, one of the group consisting of an oxygen atom, a sulfur atom, and a selenium atom is preferred, and a sulfur atom is more preferred for its high carrier mobility. Y in equations (8-1) to (8-11) is CR 61 or nitrogen atom, and for stability, CR 61 is preferred. R in equations (8-1) to (8-11) 46 ~R 61 each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 46 ~R 61 At least one of the groups is a group represented by formula (2). The definition of the group represented by formula (2) in formulas (8-1) to (8-11) is the same as that in formulas (1-I) and (1-II) above.

[0057] The R 46 ~R 61 The halogen atom in represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom because it is stable. The R 46 ~R 61Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isovaleryl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, alkyl groups having 1 to 14 carbon atoms are preferred, as they result in aromatic compounds that exhibit particularly high carrier mobility and high solubility, and linear alkyl groups having 1 to 14 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups, are more preferred. The R 46 ~R 61 Examples of the alkenyl group having 2 to 20 carbon atoms in the formula (I) include ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopentenyl-1-, cyclohexenyl-1-, and cycloheptenyl-1- groups. The R 46 ~R 61 Examples of the alkynyl group having 2 to 20 carbon atoms in the formula (I) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, and an n-dodecynyl group.

[0058] The R 46 ~R 61Examples of the alkadienyl group having 4 to 22 carbon atoms in the formula (I) include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonadienyl group, an n-decadienyl group, an n-dodecadienyl group, and an n-tridecadienyl group. An alk-1,3-dienyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-dienyl group, an n-hepta-1,3-dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, or an n-deca-1,3-dienyl group is more preferred. The R 46 ~R 61 Examples of the alkadiynyl group having 4 to 22 carbon atoms in the formula (I) include a butadiynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadiynyl group, an n-octadiynyl group, an n-nonadiynyl group, an n-decadiynyl group, an n-dodecadiynyl group, an n-tridecadiynyl group, and the like. A 1,3-alkadiynyl group having 4 to 22 carbon atoms is preferred, and a hexa-1,3-diynyl group, an n-hepta-1,3-diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, or an n-deca-1,3-diynyl group is more preferred. The R 46 ~R 61The aryl group having 4 to 26 carbon atoms in the formula (I) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; alkyl-substituted phenyl groups such as a p-tolyl group, a p-(n-hexyl)phenyl group, a p-(n-octyl)phenyl group, and a p-(2-ethylhexyl)phenyl group; a 2-furyl group; a 2-thienyl group; a 5-fluoro-2-furyl group, a 5-methyl-2-furyl group, a 5-ethyl-2-furyl group, a 5-(n-propyl)-2-furyl group, a 5-(n-butyl)-2-furyl group, a 5-(n-pentyl)-2-furyl group, and a 5-(n-hexyl)-2-furyl group. , a 5-(n-octyl)-2-furyl group, a 5-(2-ethylhexyl)-2-furyl group, a 5-fluoro-2-thienyl group, a 5-methyl-2-thienyl group, a 5-ethyl-2-thienyl group, a 5-(n-propyl)-2-thienyl group, a 5-(n-butyl)-2-thienyl group, a 5-(n-pentyl)-2-thienyl group, a 5-(n-hexyl)-2-thienyl group, a 5-(n-octyl)-2-thienyl group, and a 5-(2-ethylhexyl)-2-thienyl group.

[0059] The R 46 ~R 61 For stability, R is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2). 46 and R 47 is preferably one of the group consisting of a group represented by formula (2), a hydrogen atom, and a fluorine atom, and more preferably one of the group consisting of a group represented by formula (2) and a hydrogen atom; R 46 and R 47 It is more preferable that both of R are groups represented by formula (2). 48 ~R 61 is preferably selected from the group consisting of a hydrogen atom and a methyl group, and more preferably a hydrogen atom.

[0060] In the formulae (8-5) and (8-6), o represents 0 or 1, and 1 is preferred for high carrier mobility.

[0061] Specific examples of the compound of the present invention include the following.

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] As a method for producing the compound of the present invention, any method can be used as long as it is possible to produce the compound.

[0074] The method for producing the aromatic compound of the present invention includes, for example, 8 , X 9 is a sulfur atom, and Y 5 , Y 6 is CH and R 38 , R 41 is a group represented by formula (2), and R 39 , R 40 , R 42 , R 43 is a hydrogen atom, l and n in formula (2) are each 0, and Z 1 and Z 2 The aromatic compound (7-1a) in which is a hydrogen atom can be produced by the following process A1 to C1.

[0075] (Step A1): A method of converting a dithienobiphenylene derivative (compound 2) into a dilithium salt with butyllithium and synthesizing a dibromodithienobiphenylene derivative (compound 3) using a brominating agent. (Step B1): A method for producing alkylmagnesium bromide by reacting an alkyl bromide derivative with magnesium. (Step C1): A method for producing an aromatic compound (7-1a) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in Step B1 with the dibromodithienobiphenylene derivative (compound 3) synthesized in Step A1 in the presence of a palladium catalyst.

[0076] Details of each step are shown below. (A1 process) Step A1 is a method of producing a dibromo derivative by converting a dithienobiphenylene derivative into a dilithium salt with two or more equivalents of butyllithium and reacting the salt with a brominating agent. The dilithium salt can be prepared, for example, using 2 to 3 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, N-bromosuccinimide (hereinafter abbreviated as "NBS"), etc. can be used.

[0077] (B1 process) Step B1 is a method of producing an alkylmagnesium bromide by reacting an alkyl bromide derivative with magnesium. The magnesium salt can be prepared, for example, using 1 to 2 equivalents of magnesium in a solvent such as THF or diethyl ether at a temperature in the range of 25°C to 60°C. Examples of the alkyl bromide derivative in step B1 include benzyl bromide, 2-phenylethyl bromide, 3-phenylpropyl bromide, 4-phenylbutyl bromide, 4-methylphenethyl bromide, 1-(2-bromoethyl)-4-ethylbenzene, 1-(2-bromoethyl)-4-propylbenzene, 1-(2-bromoethyl)-4-butylbenzene, 1-(2-bromoethyl)-4-pentylbenzene, 1-(2-bromoethyl)-4-hexylbenzene, 1-(2-bromoethyl)-4-heptylbenzene, 1-(2-bromoethyl)-4-octylbenzene, and 5-(2-bromoethyl)-2,3-dihydrobenzofuran.

[0078] (C1 process) Step C1 is a method for producing an aromatic compound (7-1a) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in Step B1 with the dibromodithienobiphenylene derivative (compound 3) synthesized in Step A1 in the presence of a palladium catalyst. The alkylzinc chloride can be prepared using zinc chloride in a solvent such as THF or diethyl ether at a temperature in the range of 0°C to 25°C. Examples of the palladium catalyst in step C1 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium, and the reaction temperature can be in the range of 20°C to 60°C.

[0079] A more specific production method that is preferable because it has fewer reaction steps is shown in the following reaction scheme. [ka]

[0080] (Here, A and m have the same meanings as A and m shown in formula (2).)

[0081] Also, X in equation (7-2) 8 , X 9 is a sulfur atom, and Y 5 , Y 6 is CH and R 38 , R 41 is a group represented by formula (2), and R 39 , R 40 , R 42 , R 43 is a hydrogen atom, l and n in formula (2) are each 0, and Z 1 and Z 2 The aromatic compound (7-2a) in which is a hydrogen atom can be produced by the following process steps D1 to G1.

[0082] (Step D1): A step of preparing 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene by Sonogashira coupling of 1,5-difluoro-2,6-diiodohalobiphenylene with trimethylsilylacetylene in the presence of a palladium / copper catalyst. (Step E1): A step of reacting 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene obtained in Step D1 with sodium sulfide to produce biphenyleno[2,1-b:6,5-b']dithiophene. (Step F1): A step of converting the biphenyleno[2,1-b:6,5-b']dithiophene obtained in Step E1 into a dilithium salt with butyllithium, and then using a brominating agent to produce 2,7-dibromobiphenyleno[2,1-b:6,5-b']dithiophene. (Step G1): A process for producing an aromatic compound (7-2a) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in the aforementioned Step B1 with 2,7-dibromobiphenyleno[2,1-b:6,5-b']dithiophene synthesized in Step F1 in the presence of a palladium catalyst.

[0083] Details of each step are shown below. (D1 process) Step D1 is a step of producing 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene by Sonogashira coupling of 2,6-difluoro-1,5-diiodohalobiphenylene with trimethylsilylacetylene in the presence of a palladium catalyst and a copper catalyst. Examples of the palladium catalyst include tetrakis(triphenylphosphine)palladium and dichlorobis(triphenylphosphine)palladium, and examples of the copper catalyst include copper(I) iodide, copper(I) bromide, and copper(I) chloride. Sonogashira coupling can be carried out in a solvent such as triethylamine, diisopropylamine, diisopropylethylamine, piperidine, or pyridine at a temperature ranging from 20°C to 80°C. Toluene, THF, or the like may be added as a solvent.

[0084] (E1 process) Step E1 is a step of producing biphenyleno[2,1-b:6,5-b']dithiophene by reacting 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene obtained in Step D1 with sodium sulfide. The reaction can be carried out in a solvent such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), N,N-dimethylformamide (hereinafter abbreviated as DMF), or N-methylpyrrolidone (hereinafter abbreviated as NMP) at a temperature ranging from 20 to 200°C. This step can also be carried out using known reaction conditions for synthesizing a benzothiophene ring from a 2-haloalkynylbenzene (for example, Organic Letters, 2009, Vol. 11, pp. 2473-2475).

[0085] (F1 process) Step F1 is a method for producing a dibromo compound by converting the biphenyleno[2,1-b:6,5-b']dithiophene obtained in Step E1 into a dilithium salt with two or more equivalents of butyllithium, and then reacting the salt with a brominating agent. The dilithium salt can be prepared, for example, using 2 to 3 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, NBS, etc. can be used.

[0086] (G1 process) Step G1 is a method for producing aromatic compound (7-2a) by reacting alkylzinc chloride derived from alkylmagnesium bromide obtained in Step B1 with 2,7-dibromobiphenyleno[2,1-b:6,5-b']dithiophene synthesized in Step F1 in the presence of a palladium catalyst. The alkylzinc chloride can be prepared using zinc chloride in a solvent such as THF or diethyl ether at a temperature in the range of 0°C to 25°C. Examples of the palladium catalyst in Step G1 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium, and the reaction temperature can be in the range of 20°C to 60°C.

[0087] A more specific production method that is preferable because it has fewer reaction steps is shown in the following reaction scheme. [ka]

[0088] (Here, A and m have the same meanings as A and m shown in formula (2).)

[0089] X in equation (7-5) 8 , X 9 is a sulfur atom, and Y 5 , Y 6 is CH and R 38 , R 41 is a group represented by formula (2), and R 39 , R 40 , R 42 , R 43 , R 71 , R 72 is a hydrogen atom, l and n in formula (2) are each 0, and Z 1 and Z 2 The aromatic compound (7-5a) in which is a hydrogen atom can be produced by a method including the steps A2 below, B1 above, and C2 below.

[0090] (Step A2): A method of converting an anthradithiophene derivative (compound 19) into a dilithium salt with butyllithium and synthesizing a dibromoanthradithiophene derivative (compound 20) using a brominating agent. (Step C2): A method for producing aromatic compound (7-5a) by reacting alkylzinc bromide derived from alkylmagnesium bromide obtained in Step B1 with the dibromoanthradithiophene derivative (compound 20) synthesized in Step A2 in the presence of a palladium catalyst.

[0091] Details of each step are shown below. (A2 process) Step A2 is a method of producing a dibromo compound by converting an anthradithiophene derivative into a dilithium salt with two or more equivalents of butyllithium and reacting the salt with a brominating agent. The dilithium salt can be prepared, for example, using 2 to 3 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, etc. can be used.

[0092] (C2 process) Step C2 is a method for producing aromatic compound (7-5a) by reacting alkylzinc chloride derived from alkylmagnesium bromide obtained in Step B1 with dibromoanthradithiophene derivative (compound 20) synthesized in Step A2 in the presence of a palladium catalyst. Alkyl zinc bromide can be prepared using zinc chloride in a solvent such as THF or diethyl ether at a temperature in the range of 0°C to 25°C. Examples of the palladium catalyst in step C2 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium, and the reaction temperature can be in the range of 20°C to 60°C.

[0093] A more specific production method that is preferable because it has fewer reaction steps is shown in the following reaction scheme. [ka]

[0094] (Here, A and m have the same meanings as A and m shown in formula (2).)

[0095] X in equation (7-1) 8 , X 9 is a sulfur atom, and Y 5 , Y 6 is CH and R 38 is a group represented by formula (2), and R 39 ~R 43 is a hydrogen atom, l and n in formula (2) are each 0, and Z 1 and Z 2 The aromatic compound (7-1b) in which is a hydrogen atom can be produced by a method including the steps A3 below, B1 above, and C3 below.

[0096] (Step A3): A method of converting a dithienobiphenylene derivative (compound 2) into a monolithium salt with butyllithium and synthesizing a monobromodithienobiphenylene derivative (compound 21) using a brominating agent. (Step C3): A method for producing aromatic compound (7-1b) by reacting alkylzinc bromide derived from alkylmagnesium bromide obtained in Step B1 with the monobromodithienobiphenylene derivative (compound 21) synthesized in Step A3 in the presence of a palladium catalyst.

[0097] Details of each step are shown below. (A3 process) In step A3, a dithienobiphenylene derivative is converted into a monolithium salt with 1.0 equivalent of butyllithium, and the salt is reacted with a brominating agent to produce a monobromo derivative. The monolithium salt can be prepared, for example, using 0.5 to 1.5 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, etc. can be used.

[0098] (C3 process) Step C3 is a method for producing aromatic compound (7-1b) by reacting alkylzinc chloride derived from alkylmagnesium bromide obtained in Step B1 with monobromodithienobiphenylene derivative (compound 21) synthesized in Step A3 in the presence of a palladium catalyst. Alkyl zinc bromide can be prepared using zinc chloride in a solvent such as THF or diethyl ether at a temperature in the range of 0°C to 25°C. Examples of the palladium catalyst in step C3 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium, and the reaction temperature can be in the range of 20°C to 60°C.

[0099] A more specific production method that is preferable because it has fewer reaction steps is shown in the following reaction scheme. [ka]

[0100] (Here, A and m have the same meanings as A and m shown in formula (2).)

[0101] X in equation (7-5) 8 , X 9 is a sulfur atom, and Y 5 , Y 6 is CH and R 38 is a group represented by formula (2), and R 39 ~R 41 , R 42 , R 43 , R 71 , R 72 is a hydrogen atom, l and n in formula (2) are each 0, and Z 1 and Z2 The aromatic compound (7-5b) in which is a hydrogen atom can be isolated as a by-product in the above step C2, or can be produced by a method including the following steps A4, the above step B1, and the below step C4.

[0102] (Step A4): A method of converting an anthradithiophene derivative (compound 19) into a monolithium salt with butyllithium and synthesizing a monobromoanthradithiophene derivative (compound 22) using a brominating agent. (Step C4): A method for producing aromatic compound (7-5b) by reacting alkylzinc bromide derived from alkylmagnesium bromide obtained in Step B1 with the monobromoanthradithiophene derivative (compound 22) synthesized in Step A4 in the presence of a palladium catalyst.

[0103] Details of each step are shown below. (A4 process) In step A4, an anthradithiophene derivative is converted into a monolithium salt with one equivalent of butyllithium, and the salt is reacted with a brominating agent to produce a monobromo derivative. The monolithium salt can be prepared, for example, using 0.5 to 1.5 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, etc. can be used.

[0104] (C4 process) Step C4 is a method for producing aromatic compound (7-5b) by reacting alkylzinc chloride derived from alkylmagnesium bromide obtained in Step B1 with the monobromoanthradithiophene derivative (compound 22) synthesized in Step A4 in the presence of a palladium catalyst. Alkyl zinc bromide can be prepared using zinc chloride in a solvent such as THF or diethyl ether at a temperature in the range of 0°C to 25°C. Examples of the palladium catalyst in step C4 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium, and the reaction temperature can be in the range of 20°C to 60°C.

[0105] A more specific production method that is preferable because it has fewer reaction steps is shown in the following reaction scheme. [ka]

[0106] (Here, A and m have the same meanings as A and m shown in formula (2).)

[0107] The compound of the present invention can be dissolved in an appropriate solvent to prepare a solution for forming an organic semiconductor layer containing the compound. Any solvent can be used as the solvent as long as it can dissolve the aromatic compound represented by formula (1-I) or formula (1-II). Organic solvents with a boiling point of 100°C or higher at normal pressure are preferred, as this allows for a favorable drying rate of the solvent when forming an organic semiconductor layer. The solvent that can be used in the present invention is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, mesitylene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetralin, and indane; aromatic ethers such as anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethyl phenyl ether, butylphenyl ether, 1,2-methylenedioxybenzene, and 1,2-ethylenedioxybenzene; aromatic halogen compounds such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, and 1,4-difluorobenzene; thiophene, 3-chlorothiophene, 2-chlorothiophene, 3-methylthiophene, 2-methylthiophene, benzothiophene, 2-methylbenzothiophene, 2,3-dihydrobenzothiophene, furan, 3-methylbenzothiophene, and the like. Heteroaromatics such as furan, 2-methylfuran, 2,5-dimethylfuran, benzofuran, 2-methylbenzofuran, 2,3-dihydrobenzofuran, thiazole, oxazole, benzothiazole, benzoxazole, and pyridine; saturated hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and decalin; glycols such as dipropylene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate;Examples of suitable solvents include esters such as dimethyl phthalate, diethyl phthalate, dimethyl terephthalate, phenyl acetate, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, and γ-butyrolactone; and cyclic ethers such as THF and 2-methoxymethyltetrahydrofuran. Among these, toluene, o-xylene, mesitylene, 1,2,4-trimethylbenzene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, and 2,3-dimethylanisole are preferred because they have an appropriate drying rate. Preferred examples of the solvents include toluene, o-xylene, mesitylene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, and 2,6-dimethylanisole; and more preferred examples of the solvents include toluene, o-xylene, mesitylene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, and 2,6-dimethylanisole. The solvent used in the present invention may be one type of solvent used alone, or two or more types of solvents having different properties such as boiling point, polarity, solubility parameter, etc. may be mixed and used.

[0108] The temperature at which the aromatic compound represented by formula (1-I) or formula (1-II) is mixed and dissolved in a solvent is preferably in the range of 0 to 80°C, more preferably 10 to 60°C, in order to promote dissolution. The aromatic compound represented by formula (1-I) or formula (1-II) is preferably dissolved and mixed in an organic solvent for 1 minute to 1 hour to obtain a homogeneous solution.

[0109] In the present invention, when the concentration of the aromatic compound represented by formula (1-I) or formula (1-II) in the organic semiconductor layer-forming solution is in the range of 0.1 to 10.0 wt %, the solution is easy to handle and the efficiency in forming the organic semiconductor layer is superior. Furthermore, when the viscosity of the organic semiconductor layer-forming solution is in the range of 0.3 to 10 mPa s, the solution exhibits more suitable coatability. Furthermore, since the aromatic compound itself has moderate cohesion properties, the solution can be prepared at a relatively low temperature. Furthermore, since the solution is oxidation-resistant, it is suitable for use in the production of organic thin films by coating. In other words, since there is no need to remove air from the atmosphere, the coating process can be simplified. Furthermore, the solution can be used in a wide variety of organic thin films, including, for example, polystyrene, poly(α-methylstyrene), poly(4-methylstyrene), poly(1-vinylnaphthalene), poly(2-vinylnaphthalene), poly(styrene-block-butadiene-block-styrene), poly(styrene-block-isoprene-block-styrene), poly(vinyltoluene), poly(styrene-co-2,4-dimethylstyrene), poly(chlorostyrene), poly(styrene-co-α-methylstyrene), poly(styrene-co-butadiene), poly(ethylene-co-norbornene), polyphenylene ether, polycarbonate, polycarbazole, and polytriarylamine. Examples of suitable binders include poly(9,9-dioctylfluorene-co-dimethyltriarylamine), poly(N-vinylcarbazole), polymethyl methacrylate, poly(styrene-co-methyl methacrylate), polyethyl methacrylate, poly(n-propyl methacrylate), polyisopropyl methacrylate, poly(n-butyl methacrylate), polyphenyl methacrylate, polymethyl acrylate, polyethyl acrylate, and poly(n-propyl acrylate). Polymers such as polystyrene, poly(α-methylstyrene), poly(ethylene-co-norbornene), and polymethyl methacrylate can also be used as binders. The concentration of these polymer binders is preferably 0.001 to 10.0 wt % to achieve a suitable solution viscosity.

[0110] The glass transition temperature (Tg) of the polymer binder is preferably 105°C or higher, more preferably 120°C or higher, and particularly preferably 150°C or higher, as this is more suitable for handling process temperatures during the manufacture of electronic devices. Furthermore, since the molecular weight of the polymer is suitable for obtaining an organic thin-film transistor with higher carrier mobility, it is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 20,000 to 100,000. Note that in the present invention, the molecular weight of the polymer refers to the weight average molecular weight (Mw) in terms of polystyrene. The polymer has the effect of a general polymer binder and improves the film-forming properties of the resulting organic semiconductor layer, and insulating polymers and semiconducting polymers can also be used. Specific examples of polymers that can be used as the polymer binder in the present invention include, in addition to the polymers listed above, polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, methyl methacrylate-styrene copolymers, and the like.

[0111] More specifically, the polar cyclic polyolefin is more preferably a polymer represented by the following formula (9): [ka] (where R 62 ~R 64each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. Z represents one member of the group consisting of a halogen atom, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. p represents an integer of 20 to 5,000, and q and r each independently represent an integer of 0 to 2. A bond consisting of a solid line and a dotted line represents a single bond or a double bond. )

[0112] R in Equation (9) 62 ~R 64 each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 20 carbon atoms is preferred for high heat resistance. R 62 ~R 64In the formula (I), examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isobutyl, sec-butyl, and n-pentyl. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, p-tolyl, p-(n-hexyl)phenyl, p-(n-octyl)phenyl, and p-(2-ethylhexyl)phenyl. Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms include methyloxycarbonyl, ethyloxycarbonyl, and n-propyloxycarbonyl. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl and 4-methylphenoxycarbonyl. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, and n-propoxy. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group and a 4-methylphenoxy group. Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, and an n-propylamino group. Among these, the substituent R 60 is preferably a methyl group, an ethyl group, or an n-propyl group, and the substituent R 63 and R 64 is preferably a hydrogen atom. Z in formula (9) represents one member selected from the group consisting of a halogen atom, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms in the substituent Z include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an n-hexyloxycarbonyl group, and a cyclohexyloxycarbonyl group. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 2,4-dimethylphenoxycarbonyl group, and a 4-ethylphenoxycarbonyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group and an ethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group and a 4-methylphenoxy group. Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, and an n-propylamino group. For high solubility and high heat resistance, an alkyloxycarbonyl group having 2 to 20 carbon atoms is preferred. p represents an integer of 20 to 5,000, and is preferably 40 to 2,000 because this is suitable for obtaining an organic thin-film transistor with higher carrier mobility. q represents an integer of 0 to 2, and is preferably 1. r represents an integer of 0 to 2, and is preferably 0 or 1, and is more preferably 0. A bond consisting of a solid line and a dotted line represents a single bond or a double bond, and is preferably a single bond for thermal stability.

[0113] The polysulfones used as the polymer binder in the present invention are not particularly limited as long as they have a polysulfone structure, and more specific examples include polysulfones represented by the following polysulfones 1 to 5. [ka]

[0114] (wherein the substituent R 65 ~R 68 each independently represents an alkyl group having 1 to 20 carbon atoms, and s represents an integer of 10 to 20,000.

[0115] Substituent R 65 ~R 68Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include linear or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, and 2-hexyldecyl. s represents an integer of 10 to 20,000, and is preferably an integer of 10 to 10,000.

[0116] The acrylonitrile-styrene copolymer used as the polymer binder in the present invention is a copolymer of acrylonitrile and styrene in any ratio, and exhibits good electrical properties and improves reliability by reducing the change in threshold voltage when bias stress is applied, so the weight ratio of acrylonitrile to styrene is preferably 10:90 to 50:50, and more preferably 20:80 to 40:60. The methyl methacrylate-styrene copolymer used as the polymer binder in the present invention is a copolymer of methyl methacrylate and styrene in any ratio, and exhibits good electrical properties and improves reliability by reducing the change in threshold voltage when bias stress is applied, so the molar ratio of methyl methacrylate to styrene is preferably 1:99 to 90:10, and more preferably 1:99 to 70:30. The polymer used as the polymer binder in the present invention may have its surface energy adjusted by a surface treatment agent. A silane coupling agent may be used as the surface treatment agent, and specific examples thereof include 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, octyltrichlorosilane, β-phenethyltrichlorosilane, and β-phenethyltrimethoxysilane. The polymer used in the present invention may be a single polymer or a mixture of two or more polymers. Furthermore, polymers of different molecular weights may be mixed and used.

[0117] The coating method for forming an organic semiconductor layer using the organic semiconductor layer-forming solution of the present invention is not particularly limited as long as it is a method that can form an organic semiconductor layer, and examples thereof include simple coating methods such as spin coating, drop casting, dip coating, and cast coating; and printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among these, spin coating, drop casting, and inkjet are preferred because they enable an organic semiconductor layer to be formed easily and efficiently. After applying the solution for forming an organic semiconductor layer of the present invention, the solvent is removed by drying, whereby an organic semiconductor layer can be formed using the solution for forming an organic semiconductor layer. When the solvent is dried and removed from the applied organic semiconductor layer, the drying conditions are not particularly limited, and the solvent can be dried and removed, for example, under normal pressure or reduced pressure. There are no particular limitations on the temperature at which the organic solvent is dried and removed from the applied organic semiconductor layer, but it is preferable to perform the drying and removal at a temperature in the range of 10 to 150°C, as this allows the organic solvent to be dried and removed efficiently from the applied organic semiconductor layer and enables the formation of an organic semiconductor layer. When the organic solvent is dried and removed from the applied organic semiconductor layer, the crystal growth of the aromatic compound represented by formula (1-I) or formula (1-II) can be controlled by adjusting the evaporation rate of the organic solvent being removed.

[0118] There is no limitation on the thickness of the organic semiconductor layer formed by the organic semiconductor layer-forming solution of the present invention, and it is preferably in the range of 1 nm to 1 μm, more preferably in the range of 10 nm to 300 nm, since good carrier mobility can be obtained. The resulting organic semiconductor layer may be subjected to annealing treatment at 40 to 180° C. after the organic semiconductor layer is formed. The organic semiconductor layer formed from the organic semiconductor layer-forming solution of the present invention can be used as an organic semiconductor device comprising the organic semiconductor layer, particularly as an organic thin film transistor comprising the organic semiconductor layer.

[0119] An organic thin-film transistor can be obtained by laminating an organic semiconductor layer provided with a source electrode and a drain electrode and a gate electrode on a substrate via an insulating layer. By using an organic semiconductor layer formed using the organic semiconductor layer-forming solution of the present invention as the organic semiconductor layer, it is possible to obtain an organic thin-film transistor that exhibits excellent semiconducting and electrical properties. The cross-sectional structure of a typical organic thin-film transistor is shown in Figure 1. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type organic thin-film transistor, in which 1 is an organic semiconductor layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode, and the organic semiconductor layer formed from the organic semiconductor layer-forming solution of the present invention can be applied to any of these organic thin-film transistors.

[0120] The substrate used in the present invention is not particularly limited, and examples thereof include plastic substrates such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefins, fluorinated cyclic polyolefins, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, and cellulose triacetate; inorganic substrates such as glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. When highly doped silicon is used as the substrate, the substrate can also serve as the gate electrode. The gate electrode according to the present invention is not particularly limited, and examples thereof include inorganic materials such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, graphene, and carbon nanotubes; and organic materials such as doped conductive polymers (e.g., PEDOT-PSS). The inorganic materials described above can also be used without any problems as metal nanoparticle inks. In this case, the solvent is preferably a polar solvent such as water, methanol, ethanol, 2-propanol, 1-butanol, or 2-butanol; an aliphatic hydrocarbon solvent having 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, or tetradecane; or an aromatic hydrocarbon solvent having 7 to 14 carbon atoms such as toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene, cyclohexylbenzene, tetralin, indane, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2-dimethylanisole, 2,3-dimethylanisole, or 3,4-dimethylanisole, for adequate dispersibility. After application, the nanoparticle ink is preferably annealed at a temperature between 80°C and 200°C to improve conductivity. The gate insulating layer according to the present invention is not particularly limited, and examples thereof include inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate; polymethyl methacrylate, polymethyl acrylate, polyimide, polyamic acid polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), polyethylene terephthalate, polyethylene naphthalate, polyethyl cinnamate, polymethyl cinnamate, poly(methyl cinnamate), ... Examples of suitable polymer insulating materials include ethyl protonate, polyethersulfone, polypropylene-co-1-butene, polyisobutylene, polypropylene, polycyclopentane, polycyclohexane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, BCB resin (trade name: Cyclotene, manufactured by Dow Chemical Company), Cytop (trademark), Teflon (trademark), and Parylene (trademark) such as Parylene C. A polymer insulating material (polymer gate insulating layer) that can be produced by a coating method is preferred because of its simple manufacturing method.

[0121] The solvent used to dissolve the polymer material is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents having 6 to 14 carbon atoms, such as hexane, heptane, octane, decane, dodecane, and tetradecane; ether solvents, such as THF, 1,2-dimethoxyethane, and dioxane; alcohol solvents, such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 2-ethylhexanol, and tetrahydrofurfuryl alcohol; ketone solvents, such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, and acetophenone; ester solvents, such as ethyl acetate, γ-butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, and tetrahydrofurfuryl propionate; amide solvents, such as DMF and NMP; Examples of suitable solvents include glycol-based solvents such as pyrene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; and fluorinated solvents such as perfluorohexane, perfluorooctane, 2-(pentafluoroethyl)hexane, and 3-(pentafluoroethyl)heptane. The concentration of the polymer insulating material is, for example, 0.1 to 10.0% by weight at a temperature of 20 to 40° C. There is no limit to the film thickness of the insulating layer obtained at this concentration, and from the viewpoint of insulation resistance, it is preferably 100 nm to 1 μm, and more preferably 150 nm to 900 nm. The surface of these gate insulating layers can be modified with, for example, silanes such as octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, and octylphosphonic acid; and silylamines such as hexamethyldisilazane. Surface treatment of the gate insulating layer generally increases the crystal grain size and improves molecular orientation of the organic semiconductor material, resulting in favorable results such as improved carrier mobility, current on / off ratio, and threshold voltage. The materials for the source and drain electrodes of the organic thin-film transistor of the present invention are not particularly limited, and can be the same as those for the gate electrode. They can be the same as or different from the gate electrode material, or different materials can be laminated. Furthermore, to improve carrier injection efficiency, these electrode materials can be subjected to a surface treatment. Examples of surface treatment agents used for the surface treatment include benzenethiol, pentafluorobenzenethiol, 4-fluorobenzenethiol, and 4-methoxybenzenethiol.

[0122] The organic thin film transistor of the present invention has a carrier mobility of 1.00 cm due to its fast operation. 2 / V·sec or more. Also, due to the high switching characteristics, the current on / off ratio is preferably 1.0×10 6 It is preferable that this is equal to or greater than this. The organic thin-film transistor of the present invention can be used in electronic materials such as organic semiconductor layers of transistors for electronic paper, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, and biosensors; organic EL display materials; organic semiconductor laser materials; organic thin-film solar cell materials; photonic crystal materials; and semiconductor materials for image sensors. Since the aromatic compound represented by formula (1-I) or formula (1-II) forms a crystalline thin film, it is preferably used as a semiconductor layer of an organic thin-film transistor. [Example]

[0123] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0124] To identify the product 1 H NMR spectroscopy and liquid chromatography-mass spectroscopy (LCMS) analysis were used. < 1 H NMR Spectroscopic Analysis Device: JEOL Ltd., (product name) Delta V5 (400MHz) Measurement temperature: 23°C (if no temperature is specified) <Liquid Chromatography-Mass Spectrometry (LCMS) Analysis> Equipment: Bruker Daltonics, (product name) microTOF focus MS ionization: atmospheric pressure chemical ionization (APCI) method LC conditions: Conditions described in the liquid chromatography analysis section below

[0125] Thin layer chromatography, gas chromatography (GC), and liquid chromatography (LC) were used to confirm the progress of the reaction. The purity of the aromatic compounds was also measured using liquid chromatography. <Thin-layer chromatography analysis> Merck PLC silica gel 60F254 0.5 mm for thin layer chromatography was used, and hexane and / or toluene were used as the developing solvent. <Gas chromatography analysis> Apparatus; manufactured by Shimadzu Corporation, (trade name) GC2014 Column; manufactured by RESTEK Corporation, (trade name) Rxi-1HT, 30 m <Liquid chromatography analysis> Apparatus; manufactured by Tosoh Corporation (controller; PX-8020, pump; CCPM-II, degasser; SD-8022) Column; manufactured by Tosoh Corporation, (trade name) ODS-100V, 5 μm, 4.6 mm × 250 mm Column temperature: 33 °C Eluent; dichloromethane:acetonitrile = 2:8 (volume ratio) Flow rate: 1.0 ml / min Detector; UV (manufactured by Tosoh Corporation, (trade name) UV-8020, wavelength; 254 nm).

[0126] The melting point of the aromatic compound was measured using a DSC (differential scanning calorimeter). <DSC measurement> Apparatus; manufactured by SII NanoTechnology Inc., model; DSC6220 Heating and cooling rate: 10 °C / min Scanning range: -10 °C to 300 °C

[0127] Synthesis Example 1 Synthesis of dibromodithieno[3,2-b:2',3'-d]biphenylene derivative (Compound 3) (Step A1) Under a nitrogen atmosphere, 89.0 mg (0.336 mmol) of the dithieno[3,2-b:2',3'-d]biphenylene derivative (Compound 2 in the said publication) synthesized by the method described in JP 2018-174322 and 9 ml of THF (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to -80 °C, 0.75 mL (1.20 mmol) of 1.6 M normal butyllithium (Tokyo Chemical Industry) was added, and after stirring for 5 minutes, it was stirred at room temperature for 25 minutes. It was cooled to -78 °C, 5 mL of a THF solution (Fuji Film Wako Pure Chemical Industries, dehydrated grade) of 436 mg (1.34 mmol) of 1,2-dibromotetrachloroethane was added, and it was stirred while warming to room temperature. Water was added, the solid was filtered, and washed with water, methanol, and hexane to obtain 122 mg of a yellow solid of the dibromodithieno[3,2-b:2',3'-d]biphenylene derivative (yield 87%). MS(APCI + ) m / z: 423(M + +H). 1 H NMR (CDCl3, 58°C): δ=7.07(d,J=7.4Hz,2H),7.05(s,2H),δ=6.65(d,J=7.4Hz,2H).

[0128] Synthesis Example 2: Synthesis of 2-phenylethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 738 mg (30.4 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 100 mL two-neck flask and stirred under vacuum for 3 hours. Under a nitrogen atmosphere, 50 mL of a solution of 3.70 g (20.0 mmol) of (2-bromoethyl)benzene (Tokyo Chemical Industry) in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added, and the mixture was stirred at room temperature for 1 hour and at 45 °C for 1.5 hours. The solid was removed by filtration to obtain a 0.4 M 2-phenylethyl magnesium bromide / THF solution.

[0129] Example 1 Synthesis of 2,7-di(2-phenylethyl)dithienobiphenylene (Compound 1) (Step C1) Under a nitrogen atmosphere, 136 mg (0.997 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 3 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 1.90 mL (0.760 mmol) of the 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and the mixture was stirred at room temperature for 14 hours to prepare a zinc reagent solution. Separately, 41.2 mg (0.0976 mmol) of the dibromodithienobiphenylene derivative synthesized in Synthesis Example 1, 5.20 mg (0.00711 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 5 hours and at 55°C for 1.5 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 5 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from hexane / toluene=12 / 7, yielding 16.0 mg of a yellow solid aromatic compound (Compound 1) (yield 35%). MS(APCI + ) m / z: 473(M + +H). 1 H NMR (CDCl3): δ=7.32-7.22(m,10H),7.00(d,J=7.4Hz,2H),6.69(s,2H),δ=6.64(d,J=7.4Hz,2H),δ=3.11(t,J=7.4Hz,4H),δ=3.03(t,J=7.4Hz,4H). Melting point: 195℃ (Compound 1) [ka]

[0130] Synthesis Example 3 1,4-Dibromo-2,5-bis(trimethylsilylethynyl)benzene Under a nitrogen atmosphere, 2.62 g (5.36 mmol) of 1,4-dibromo-2,5-diiodobenzene (Tokyo Chemical Industry Co., Ltd.), 55.8 mg (0.0794 mmol) of bis(triphenylphosphine)dichloropalladium (Fujifilm Wako Pure Chemical Industries, Ltd.), 20.9 mg (0.110 mmol) of copper(I) iodide (Fujifilm Wako Pure Chemical Industries, Ltd.), 10 mL of toluene (Fujifilm Wako Pure Chemical Industries, dehydrated grade), and 5 mL of triethylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 100 mL Schlenk reaction vessel. 1.67 g (17.0 mmol) of trimethylsilylacetylene (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the mixture and stirred at room temperature (25 °C) for 50 hours. The resulting reaction mixture was cooled on ice and quenched by the addition of 1 M hydrochloric acid. The toluene extract was then extracted, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 1.14 g of the target solid (yield: 50%). 1 H NMR (CDCl3): δ=7.67(s,2H),0.27(s,18H).

[0131] Synthesis Example 4 1,4-bis(5-octylthiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene Under a nitrogen atmosphere, 833 mg (3.02 mmol) of 2-bromo-5-octylthiophene (Tokyo Chemical Industry Co., Ltd.) and 6 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk reaction vessel. The solution was cooled on ice, and 1.6 mL (3.2 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0°C for 220 minutes to prepare a 5-octylthiophen-2-ylmagnesium chloride solution. Meanwhile, under a nitrogen atmosphere, 527 mg (3.86 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 7 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel and cooled to 0°C. The previously prepared 5-octylthiophen-2-yl magnesium chloride solution was added dropwise to the resulting white fine slurry solution using a Teflon (registered trademark) cannula, and the 100 ml Schlenk reaction vessel and Teflon (registered trademark) cannula were then washed with 2 ml of THF (dehydrated grade). The resulting mixture was stirred while gradually warming to room temperature. To the resulting slurry of 5-octylthiophen-2-ylzinc chloride, 400 mg (0.933 mmol) of 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 3 and 24.0 mg (0.0207 mmol, 2.2 mol % relative to 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene) of tetrakis(triphenylphosphine)palladium (Tokyo Chemical Industry Co., Ltd.) were added as a catalyst. The reaction was carried out at 60°C for 11 hours, after which the vessel was cooled with water and 1 M hydrochloric acid was added to terminate the reaction. Toluene was added, and the organic phase was separated. The organic phase was washed with water and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 20 / 1). 541 mg of a yellow solid of 1,4-bis(5-octylthiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene was obtained (yield 87%). 1 H NMR(CDCl3):δ=7.68(s,2H),7.52(d,J=3.7Hz,2H),6.74(d,J=3.7Hz,2H),2.83(t,J =7.8Hz,4H),1.71(m,4H),1.43~1.28(m,20H),0.90(t,J=7.3Hz,6H),0.27(s.18H).

[0132] Synthesis Example 5 1,4-bis(5-octylthiophen-2-yl)-2,5-diethynylbenzene Under a nitrogen atmosphere, 540 mg (0.819 mmol) of 1,4-bis(5-octylthiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 4, 7 mL of THF, 3.5 mL of methanol, and 45.8 mg (0.331 mmol) of potassium carbonate were added to a 100 mL Schlenk reaction vessel. This mixture was stirred at room temperature for 3 hours. The resulting reaction mixture was cooled on ice, and the reaction was quenched by the addition of 1 M hydrochloric acid. Toluene was added, and the organic phase was separated. The organic phase was washed twice with water and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure to obtain 422 mg of a yellow solid, 1,4-bis(5-octylthiophen-2-yl)-2,5-diethynylbenzene (quantitative). 1 H NMR(CDCl3):δ=7.71(s,2H),7.50(d,J=3.6Hz,2H),6.76(d,J=3.5Hz,2H),3.37(s, 2H), 2.83 (t, J=7.8Hz, 4H), 1.71 (m, 4H), 1.43~1.22 (m, 20H), 0.89 (t, J=7.0Hz, 6H).

[0133] Synthesis Example 6 2,8-Dioctylanthra[1,2-b:5,6-b']dithiophene Under a nitrogen atmosphere, 190 mg (0.370 mmol) of 1,4-bis(5-octylthiophen-2-yl)-2,5-diethynylbenzene (synthesized in Synthesis Example 5), 6 mL of N,N-dimethylformamide, and 20.4 mg of platinum chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 50 mL Schlenk reaction vessel. The resulting mixture was stirred at 80°C for 4 hours, and the solvent was then removed under reduced pressure. The residue was purified by silica gel column chromatography (solvent: hexane:toluene = 10:1). Further purification was performed twice by recrystallization from hexane / toluene = 4:1, yielding 82 mg of a reddish-yellow solid, 2,8-dioctylanthra[1,2-b:5,6-b']dithiophene (yield 43%). 1H NMR(CDCl3):δ=8.58(s,2H),7.83(d,J=8.7Hz,2H),6.69(d,J=8.7Hz,2H),7.14(s, 2H), 3.00 (t, J=7.6Hz, 4H), 1.81 (m, 4H), 1.45~1.22 (m, 20H), 0.90 (t, J=7.0Hz, 6H). Melting point: 124°C (2,8-dioctylanthra[1,2-b:5,6-b']dithiophene) [ka]

[0134] Example 2 (Preparation of solution for forming organic semiconductor layer) In air, 0.87 mg of 2,7-di(2-phenylethyl)dithienobiphenylene (Compound 1) synthesized in Example 1 and 434 mg of toluene (Fujifilm Wako Pure Chemical Industries, Pure Grade) were added to a 10 ml sample tube, heated to 50°C for dissolution, and then allowed to cool to room temperature (25°C) to prepare a solution for forming an organic semiconductor layer. The solution remained in solution even after 10 hours at 25°C (Compound 1 concentration: 0.20 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0135] Example 3 (Fabrication of organic semiconductor layer and organic thin film transistor) A top gate-bottom contact type p-type organic thin film transistor was fabricated using the organic semiconductor layer forming solution obtained in Example 2. The materials of each component and the film formation method are shown in Table 1. [Table 1] The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 1.45 cm 2 / V·sec, current on / off ratio is 1.6×10 6 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing at 130°C for 10 minutes. The carrier mobility of the hole was 1.40 cm 2 / V·sec, current on / off ratio is 1.2×10 6 Almost no deterioration in performance due to heat treatment was observed.

[0136] Example 4 (Fabrication of organic semiconductor layer and organic thin film transistor) Using the organic semiconductor layer-forming solution obtained in Example 2 and the materials and film-forming method for each component shown in Example 3, a bottom-gate-bottom-contact type p-type organic thin-film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 2.29 cm 2 / V·sec, current on / off ratio is 1.5×10 6 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing at 130°C for 10 minutes. The carrier mobility of the hole was 2.25 cm 2 / V·sec, current on / off ratio is 1.0×10 6 Almost no deterioration in performance due to heat treatment was observed.

[0137] Synthesis Example 7: Synthesis of 4-propylbenzeneethanol Under a nitrogen atmosphere, 5.03 g (25.3 mmol) of 1-bromo-4-propylbenzene (Tokyo Chemical Industry Co., Ltd.) and 80 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 19.0 mL (30.4 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at -78 °C for 90 minutes. 25.0 mL (30.0 mmol) of 1.2 M ethylene oxide in THF (Tokyo Chemical Industry Co., Ltd.) was added at -78 °C and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, followed by the addition of diethyl ether to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 2.55 g of a colorless liquid, 4-propylbenzeneethanol (yield: 58%). 1H NMR (CDCl3): δ=7.11(s,4H),3.85(m,2H),2.85(t,J=6.5Hz,2H),2.57(t,J=7.5Hz,2H),1.69-1.59(m,2H),1.51-1.47(m,1H),0.95(t,J=7.3Hz,3H).

[0138] Synthesis Example 8 Synthesis of 1-(2-bromoethyl)-4-propylbenzene Under a nitrogen atmosphere, 1.07 g (6.54 mmol) of 4-propylbenzeneethanol synthesized in Synthesis Example 7 and 30 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL two-neck flask. The solution was ice-cooled, and 0.60 mL (6.32 mmol) of phosphorus tribromide was added. The mixture was stirred for 20 minutes, followed by 22 hours at room temperature. The reaction solution was poured onto ice and neutralized with saturated aqueous sodium bicarbonate. Dichloromethane was then added to separate the phases. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 489 mg of 1-(2-bromoethyl)-4-propylbenzene as a colorless liquid (yield: 33%). 1 H NMR(CDCl3):δ=7.13(s,4H),3.56(t,J=7.7Hz,2H),3.14(t,J=7.7Hz,2H),2. 57(t,J=7.6Hz,2H),1.64(dt,J=7.6Hz,J=7.3Hz,2H),0.95(t,J=7.3Hz,3H).

[0139] Synthesis Example 9 Synthesis of 2-(4-propylphenyl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 42.1 mg (1.73 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 100 mL two-neck flask and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 5 mL of a solution of 231 mg (1.02 mmol) of 1-(2-bromoethyl)-4-propylbenzene synthesized in Synthesis Example 8 in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added, and the mixture was stirred at room temperature for 90 minutes and at 40°C for 1 hour. The solid was removed by filtration to obtain a 0.2 M solution of 2-(4-propylphenyl)ethyl magnesium bromide in THF.

[0140] Example 5 Synthesis of 2,7-di(2-(4-propylphenyl)ethyl)dithienobiphenylene (Compound 4) (Step C1) Under a nitrogen atmosphere, 169 mg (1.24 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 5.00 mL (1.00 mmol) of the 0.2 M 2-(4-propylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 9 was added, and the mixture was stirred under ice cooling for 30 minutes and then at room temperature for 14 hours to prepare a zinc reagent solution. Separately, 51.0 mg (0.121 mmol) of the dibromodithienobiphenylene derivative synthesized in Synthesis Example 1, 8.60 mg (0.0131 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 6 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from toluene to obtain 43.6 mg of a yellow solid of 2,7-di(2-(4-propylphenyl)ethyl)dithienobiphenylene (Compound 4) (yield: 65%). 1H NMR(CDCl3):δ=7.13(m,8H),6.99(d,J=7.6Hz,2H),6.69(s,2H),6.64(d,J=7.6Hz,2H),3.09(t,J=6.7Hz, 4H), 2.99(t,J=6.7Hz,4H),2.57(t,J=7.4Hz,4H),1.64(dt,J=7.4Hz,J=7.2Hz,4H),0.95(t,J=7.2Hz,6H). Melting point: 230℃ (Compound 4) [ka]

[0141] Synthesis Example 10: Synthesis of 4-butylbenzeneethanol Under a nitrogen atmosphere, 4.34 g (20.4 mmol) of 1-bromo-4-butylbenzene (Tokyo Chemical Industry Co., Ltd.) and 80 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 26.0 mL (41.6 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at -78 °C for 2 hours. 25.0 mL (30.0 mmol) of 1.2 M ethylene oxide in THF (Tokyo Chemical Industry Co., Ltd.) was added at -78 °C and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, followed by the addition of diethyl ether to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent; hexane:dichloromethane = 1 / 1 to 0 / 1, ethyl acetate) to obtain 2.20 g of a colorless liquid, 4-butylbenzeneethanol (yield: 60%). 1 H NMR (CDCl3): δ=7.14(s,4H),3.85(m,2H),2.84(t,J=6.5Hz,2H),2.59(t,J=7.8Hz,2H),1.63-1.56(m,2H),1.41-1.32(m,1H),0.93(t,J=7.3Hz,3H).

[0142] Synthesis Example 11 Synthesis of 1-(2-bromoethyl)-4-butylbenzene Under a nitrogen atmosphere, 2.20 g (12.3 mmol) of 4-butylbenzeneethanol synthesized in Synthesis Example 10 and 30 ml of dichloromethane (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 ml two-neck flask. The solution was ice-cooled, and 2.40 ml (25.2 mmol) of phosphorus tribromide was added. The mixture was stirred for 10 minutes, followed by 25 hours at room temperature. The reaction solution was poured onto ice and neutralized with saturated aqueous sodium bicarbonate. Dichloromethane was then added to separate the phases. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 922 mg of a colorless liquid, 1-(2-bromoethyl)-4-butylbenzene (yield: 31%). 1 H NMR(CDCl3):δ=7.13(m,4H),3.56(t,J=7.7Hz,2H),3.14(t,J=7.7Hz,2H),2.59 (t,J=7.7Hz,2H),1.61-1.57(m,2H),1.41-1.31(m,2H),0.93(t,J=7.3Hz,3H).

[0143] Synthesis Example 12: Synthesis of 2-(4-butylphenyl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 41.2 mg (1.69 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 100 mL two-neck flask and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 5 mL of a solution of 248 mg (1.03 mmol) of 1-(2-bromoethyl)-4-butylbenzene (synthesized in Synthesis Example 11) in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added, and the mixture was stirred at room temperature for 30 minutes and at 40°C for 1 hour. The solid was removed by filtration to obtain a 0.2 M solution of 2-(4-butylphenyl)ethyl magnesium bromide in THF.

[0144] Example 6 Synthesis of 2,7-di(2-(4-butylphenyl)ethyl)dithienobiphenylene (Compound 5) (Step C1) Under a nitrogen atmosphere, 189 mg (1.39 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 5.00 mL (1.00 mmol) of the 0.2 M 2-(4-butylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 12 was added, and the mixture was stirred under ice cooling for 30 minutes and then at room temperature for 17 hours to prepare a zinc reagent solution. Separately, 50.6 mg (0.120 mmol) of the dibromodithienobiphenylene derivative synthesized in Synthesis Example 1, 9.40 mg (0.0128 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 6 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula and stirred at room temperature for 4 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from hexane / toluene=1 / 1 to obtain 37.4 mg of a yellow solid of 2,7-di(2-(4-butylphenyl)ethyl)dithienobiphenylene (Compound 5) (yield 53%). 1 H NMR(CDCl3):δ=7.12(m,8H),6.99(d,J=7.4Hz,2H),6.69(s,2H),6.64(d,J=7.4Hz,2H),3.09(t,J=6.6Hz,4H ),2.99(t,J=6.6Hz,4H),2.59(t,J=7.7Hz,4H),1.61-1.57(m,4H),1.40-1.31(m,4H),0.93(t,J=7.3Hz,6H). Melting point: 211°C (Compound 5) [ka]

[0145] Synthesis Example 13: Synthesis of 4-heptylbenzeneethanol Under a nitrogen atmosphere, 5.18 g (20.3 mmol) of 1-bromo-4-heptylbenzene (Tokyo Chemical Industry Co., Ltd.) and 80 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 26.0 mL (41.6 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at -78 °C for 4 hours. 25.0 mL (30.0 mmol) of 1.2 M ethylene oxide in THF (Tokyo Chemical Industry Co., Ltd.) was added at -78 °C and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, followed by the addition of diethyl ether to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane, ethyl acetate) to obtain 3.30 g of a colorless liquid, 4-heptylbenzeneethanol (74% yield). 1 H NMR(CDCl3):δ=7.14(s,4H),3.85(m,2H),2.85(t,J=6.6Hz,2H),2.58(t,J= 7.6Hz, 2H), 1.60 (m, 2H), 1.46 (bs, 1H), 1.30 (m, 8H), 0.89 (t, J=6.8Hz, 3H).

[0146] Synthesis Example 14: Synthesis of 1-(2-bromoethyl)-4-heptylbenzene Under a nitrogen atmosphere, 3.15 g (14.3 mmol) of 4-heptylbenzeneethanol synthesized in Synthesis Example 13 and 30 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL two-neck flask. The solution was ice-cooled, and 1.40 mL (14.7 mmol) of phosphorus tribromide was added. The mixture was stirred for 30 minutes, followed by 19 hours at room temperature. The reaction solution was poured onto ice and neutralized with saturated aqueous sodium bicarbonate. Dichloromethane was then added to separate the phases. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 1.74 g of 1-(2-bromoethyl)-4-heptylbenzene as a colorless liquid (43% yield). 1H NMR (CDCl3): δ=7.12(m,4H),3.56(t,J=7.4Hz,2H),3.13(t,J=7.4Hz,2H),2.58(t,J=7.6Hz,2H),1.60(m,2H),1.30(m,8H),0.88(t,J=7.0Hz,3H).

[0147] Synthesis Example 15: Synthesis of 2-(4-heptylphenyl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 42.1 mg (1.73 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 100 mL two-neck flask and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) solution of 288 mg (1.02 mmol) of 1-(2-bromoethyl)-4-heptylbenzene synthesized in Synthesis Example 14 was added, and the mixture was stirred at room temperature for 40 minutes and at 40°C for 1 hour. The solid was removed by filtration to obtain a 0.2 M 2-(4-heptylphenyl)ethyl magnesium bromide / THF solution.

[0148] Example 7 Synthesis of 2,7-di(2-(4-heptylphenyl)ethyl)dithienobiphenylene (Compound 6) (Step C1) Under a nitrogen atmosphere, 190 mg (1.40 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 5.00 mL (1.00 mmol) of the 0.2 M 2-(4-heptylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 15 was added, and the mixture was stirred under ice cooling for 1 hour and at room temperature for 16 hours to prepare a zinc reagent solution. Separately, 49.8 mg (0.118 mmol) of the dibromodithienobiphenylene derivative synthesized in Synthesis Example 1, 9.60 mg (0.0131 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 6 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 23 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from hexane / toluene=1 / 1 to obtain 36.1 mg of a yellow solid of 2,7-di(2-(4-heptylphenyl)ethyl)dithienobiphenylene (Compound 6) (yield 46%). 1 H NMR(CDCl3):δ=7.12(m,8H),6.99(d,J=7.5Hz,2H),6.69(s,2H),6.64(d,J=7.5Hz,2H),3.09(t,J=6.8H z,4H),2.99(t,J=6.8Hz,4H),2.58(t,J=7.6Hz,4H),1.60(m,4H),1.31(m,16H),0.88(t,J=7.1Hz,6H). Melting point: 198℃ (Compound 6) [ka]

[0149] Synthesis Example 16: Synthesis of 2-(2,3-dihydrobenzofuran-5-yl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 369 mg (15.2 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 100 mL two-neck flask and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 25 mL of a solution of 2.27 g (10.0 mmol) of 5-(2-bromoethyl)-2,3-dihydrobenzofuran (Tokyo Chemical Industry) in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added, and the mixture was stirred at room temperature for 1 hour and at 40 °C for 1 hour. The solid was removed by filtration to obtain a 0.4 M solution of 2-(2,3-dihydrobenzofuran-5-yl)ethyl magnesium bromide in THF.

[0150] Example 8 Synthesis of aromatic compound (compound 7) (Step C1) Under a nitrogen atmosphere, 173 mg (1.30 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. 2.50 mL (1.00 mmol) of the 0.4 M 2-(2,3-dihydrobenzofuran-5-yl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 16 was added under ice cooling, and the mixture was stirred under ice cooling for 30 minutes and at room temperature for 16 hours to prepare a zinc reagent solution. Separately, 50.8 mg (0.120 mmol) of the dibromodithienobiphenylene derivative (Compound 3) synthesized in Synthesis Example 1, 10.4 mg (0.0142 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 8 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 2 to 0 / 1). The resulting solid was rinsed with methanol and purified by recrystallization from toluene to obtain 4.0 mg of a yellow solid aromatic compound (Compound 7) (yield: 6%). (Compound 7) [ka]

[0151] Synthesis Example 17: Synthesis of 2-(1,2-methylenedioxybenzene-4-yl)ethanol Under a nitrogen atmosphere, 4.03 g (20.1 mmol) of 4-bromo-1,2-methylenedioxybenzene (Tokyo Chemical Industry Co., Ltd.) and 80 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 26.0 mL (41.6 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at -78 °C for 4 hours. 25.0 mL (30.0 mmol) of 1.2 M ethylene oxide in THF (Tokyo Chemical Industry Co., Ltd.) was added at -78 °C, and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, followed by the addition of diethyl ether to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane, ethyl acetate) to obtain 2.91 g of a colorless liquid of 2-((1,2-methylenedioxybenzene-4-yl)ethanol (yield: 72%). 1 H NMR (CDCl3): δ=6.76(d,J=7.8Hz,1H),6.72(s,1H),6.68(d,J=7.8Hz,1H),5.94(s,2H),3.82(m,2H),2.79(t,J=6.4Hz,2H),1.43(m,1H).

[0152] Synthesis Example 18: Synthesis of 4-(2-bromoethyl)-1,2-methylenedioxybenzene Under a nitrogen atmosphere, 2.78 g (16.7 mmol) of 2-(1,2-methylenedioxybenzene-4-yl)ethanol (synthesized in Synthesis Example 17) and 20 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL two-neck flask. The solution was ice-cooled, and 1.60 mL (16.8 mmol) of phosphorus tribromide was added. The mixture was stirred for 30 minutes, followed by 20 hours at room temperature. The reaction solution was poured onto ice, neutralized with saturated aqueous sodium bicarbonate, and then dichloromethane was added to separate the phases. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane / hexane = 1:5) to obtain 1.03 g of a colorless liquid, 4-(2-bromoethyl)-1,2-methylenedioxybenzene (yield: 33%). 1 H NMR (CDCl3): δ=6.76(d,J=7.9Hz,1H),6.69(s,1H),6.66(d,J=7.9Hz,1H),5.95(s,2H),2.52(t,J=7.6Hz,2H),3.08(t,J=7.6Hz,2H).

[0153] Synthesis Example 19: Synthesis of 2-(1,2-methylenedioxybenzene-4-yl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 39.1 mg (1.61 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 100 mL two-neck flask and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) solution of 229 mg (1.00 mmol) of 4-(2-bromoethyl)-1,2-methylenedioxybenzene synthesized in Synthesis Example 18 was added, and the mixture was stirred at room temperature for 30 minutes and at 40°C for 1 hour. The solid was removed by filtration to obtain a 0.2 M 2-(1,2-methylenedioxybenzene-4-yl)ethyl magnesium bromide / THF solution.

[0154] Example 9 Synthesis of aromatic compound (compound 8) (step C1) Under a nitrogen atmosphere, 187 mg (1.38 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 5.0 mL (1.00 mmol) of the 0.2 M 2-(1,2-methylenedioxybenzene-4-yl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 19 was added, and the mixture was stirred under ice cooling for 1 hour and at room temperature for 15 hours to prepare a zinc reagent solution. Separately, 50.6 mg (0.112 mmol) of the dibromodithienobiphenylene derivative (Compound 3) synthesized in Synthesis Example 1, 10.8 mg (0.0148 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 8 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 2 to 0 / 1). The resulting solid was rinsed with methanol and purified by recrystallization from toluene to obtain 34.7 mg of a yellow solid aromatic compound (Compound 8) (yield: 55%). (Compound 8) [ka]

[0155] Synthesis Example 20: Synthesis of 1,4-bis(thiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene Under a nitrogen atmosphere, 8.18 g (50.2 mmol) of 2-bromothiophene (Tokyo Chemical Industry Co., Ltd.) and 90 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 mL Schlenk reaction vessel. The solution was cooled on ice, and 28.0 mL (56.0 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0°C for 3 hours to prepare a thiophen-2-ylmagnesium chloride solution. Meanwhile, under a nitrogen atmosphere, 9.31 g (68.3 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 110 ml of THF (dehydrated grade) were added to a 500 ml Schlenk reaction vessel and cooled to 0°C. The previously prepared thiophen-2-yl magnesium chloride solution was added dropwise to the resulting white fine slurry solution using a Teflon (registered trademark) cannula, and the 100 ml Schlenk reaction vessel and Teflon (registered trademark) cannula were then washed with 40 ml of THF (dehydrated grade). The resulting mixture was stirred while gradually warming to room temperature. To the resulting thiophen-2-ylzinc chloride slurry, 6.56 g (15.3 mmol) of 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 3 and 515 mg (0.445 mmol, 2.9 mol % relative to 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene) of tetrakis(triphenylphosphine)palladium (Tokyo Chemical Industry Co., Ltd.) were added as a catalyst. The reaction was carried out at 60°C for 7 hours, after which the vessel was cooled with water and 1 M hydrochloric acid was added to terminate the reaction. Toluene was added, and the organic phase was separated. The organic phase was washed with water and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 10). 5.4 g of 1,4-bis(thiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene was obtained as a yellow solid (yield: 82%). 1H NMR (CDCl3): δ=7.74(s,2H),7.70(dd,J=1.4Hz,J=3.7Hz,2H),7.37(dd,J=1.3Hz,J=5.1Hz,2H),7.09(dd,J=3.7Hz,J=5.1Hz,2H),0.26(s,18H).

[0156] Synthesis Example 21: Synthesis of 1,4-bis(thiophen-2-yl)-2,5-diethynylbenzene Under a nitrogen atmosphere, 5.38 g (12.4 mmol) of 1,4-bis(thiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 20, 100 mL of THF, 50 mL of methanol, and 801 mg (5.79 mmol) of potassium carbonate were added to a 300 mL recovery flask. This mixture was stirred at room temperature for 6 hours. The resulting reaction mixture was cooled on ice, and the reaction was quenched by the addition of 1 M hydrochloric acid. Toluene was added, and the organic phase was separated. The organic phase was washed twice with water and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure to obtain 3.53 g of a yellow solid, 1,4-bis(thiophen-2-yl)-2,5-diethynylbenzene (quantitative). 1 H NMR (CDCl3): δ=7.78(s,2H),7.67(dd,J=1.3Hz,J=3.7Hz,2H),7.39(dd,J=1.0Hz,J=5.1Hz,2H),7.12(dd,J=3.7Hz,J=5.1Hz,2H),3.37(s,2H).

[0157] Synthesis Example 22: Synthesis of anthra[1,2-b:5,6-b']dithiophene (Compound 19) Under a nitrogen atmosphere, 1.74 g (6.00 mmol) of 1,4-bis(thiophen-2-yl)-2,5-diethynylbenzene (synthesized in Synthesis Example 21), 60 mL of N,N-dimethylformamide, and 323 mg (1.21 mmol) of platinum chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 200 mL Schlenk reaction vessel. The resulting mixture was stirred at 80°C for 4 hours, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (solvent: hexane:toluene = 10 / 1 to 2 / 1) to obtain 701 mg of a yellow solid, anthra[1,2-b:5,6-b']dithiophene (Compound 19) (yield: 40%). 1 H NMR (CDCl3): δ=8.73(s,2H),7.92(d,J=8.9Hz,2H),7.84(d,J=8.9Hz,2H),7.56(d,J=5.4Hz,2H),7.56(d,J=5.4Hz,2H).

[0158] Synthesis Example 23 Synthesis of 2,8-dibromoanthra[1,2-b:5,6-b']dithiophene (Compound 20) (Step A-2) Under a nitrogen atmosphere, 602 mg (2.07 mmol) of anthra[1,2-b:5,6-b']dithiophene (Compound 19) synthesized in Synthesis Example 22 and 50 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 6.00 mL (9.60 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry) was added. The mixture was stirred for 20 minutes, followed by stirring at room temperature for 50 minutes. The mixture was then cooled to -78 °C, and 25 mL of a THF solution (Fujifilm Wako Pure Chemical Industries, dehydrated grade) of 3.45 g (10.6 mmol) of 1,2-dibromotetrachloroethane was added. The mixture was stirred while warming to room temperature. Water was added, and the solid was filtered and washed with water, methanol, and hexane to obtain 761 mg of a yellow solid of 2,8-dibromoanthra[1,2-b:5,6-b']dithiophene (Compound 20) (yield: 82%). 1 H NMR (CDCl3, 50℃): δ=8.53(s,2H),7.87(d,J=8.9Hz,2H),7.87(d,J=8.9Hz,2H),7.47(s,2H).

[0159] Example 10 Synthesis of 2,8-di(2-phenylethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 10) (Step C2) Under a nitrogen atmosphere, 413 mg (3.02 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 5.60 mL (2.34 mmol) of the 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and the mixture was stirred at 0°C for 40 minutes and at room temperature for 16 hours to prepare a zinc reagent solution. Separately, 156 mg (0.348 mmol) of 2,8-dibromoanthra[1,2-b:5,6-b']dithiophene (Compound 20) synthesized in Synthesis Example 23, 48.5 mg (0.0662 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 20 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was cooled on ice, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 5 / 1). The resulting solid was rinsed with methanol and purified by recrystallization from toluene to obtain 73.2 mg of a yellow solid of 2,8-di(2-phenylethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 10) (yield: 42%). 1 H NMR (CDCl3): δ=8.59(s,2H),7.85(d,J=8.8Hz,2H),7.69(d,J=8.8Hz,2H),7.28(m,10H),7.14(s,2H),3.34(t,J=7.6Hz,4H),3.15(t,J=7.6Hz,4H). Melting point: 221°C (Compound 10) [ka]

[0160] Example 11 Synthesis of 2-(2-phenylethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 15) (Step C2) Another component obtained by silica gel column chromatography in Example 10 was purified by recrystallization from hexane to obtain 2.0 mg of a yellow solid, 2-(2-phenylethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 15) (yield 1.5%). 1 H NMR(CDCl3):δ=8.70(s,1H),8.62(s,1H),7.90(d,J=8.6Hz,1H),7.88(d,J=8.4Hz,1H),7.82(d,J=8.7Hz,1H),7.71(d,J=8.8 Hz,1H),7.54(d,J=5.1Hz,1H),7.49(d,J=5.4Hz,1H),7.30(m,5H),7.15(s,1H),3.34(t,J=7.7Hz,4H),3.16(t,J=7.3Hz,4H). Melting point: 174°C (Compound 15) [ka]

[0161] Example 12 Synthesis of 2,8-di(2-(4-n-butylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 11) (Step C2) Under a nitrogen atmosphere, 194 mg (1.42 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 4.5 mL (0.90 mmol) of the 0.2 M 2-(4-butylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 12 was added, and the mixture was stirred at 0°C for 30 minutes and at room temperature for 16 hours to prepare a zinc reagent solution. Separately, a 100 mL Schlenk flask was charged with 39.7 mg (0.0886 mmol) of 2,8-dibromoanthra[1,2-b:5,6-b']dithiophene (Compound 20) synthesized in Synthesis Example 23, 7.96 mg (0.0109 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 3 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade). The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 5 / 1). The resulting solid was rinsed with methanol and purified by recrystallization from hexane / toluene (6 / 5), yielding 12.6 mg of a yellow solid, 2,8-di(2-(4-normal-butylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 11) (yield: 23%). 1 H NMR(CDCl3):δ=8.59(s,2H),7.85(d,J=8.7Hz,2H),7.69(d,J=8.9Hz,2H),7.19(d,J=8.0Hz,2H),7.15(s,2H),7.13(d,J=8.0 Hz,2H),3.32(t,J=7.5Hz,4H),3.12(t,J=8.5Hz,4H),2.61(t,J=7.6Hz,4H),1.61(m,4H),1.37(m,4H),0.94(t,J=7.3Hz,6H). Melting point: 227°C (Compound 11) [ka]

[0162] Example 13 Synthesis of 2-(2-(4-n-butylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 17) (Step C2) Another component obtained by silica gel column chromatography in Example 12 was purified by recrystallization from hexane to obtain 5.8 mg of a yellow solid, 2-(2-(4-normal-butylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 17) (yield: 15%). 1 H NMR(CDCl3):δ=8.70(s,1H),8.62(s,1H),7.89(d,J=8.5Hz,1H),7.87(d,J=8.0Hz,1H),7 .82(d,J=8.8Hz,1H),7.71(d,J=8.8Hz,1H),7.54(d,J=5.4Hz,1H),7.49(d,J=5.1Hz,1H) ,7.19(d,J=8.0Hz,2H),7.16(s,1H),7.13(d,J=8.1Hz,2H),3.32(t,J=7.4Hz,2H),3.12( t,J=8.6Hz,2H),2.61(t,J=7.7Hz,2H),1.60(m,2H),1.37(m,2H),0.94(t,J=7.3Hz,3H). Melting point: 161°C (Compound 17) [ka]

[0163] Example 14 Synthesis of 2,8-di(2-(4-normal-heptylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 12) (Step C2) Under a nitrogen atmosphere, 124 mg (0.909 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 3.4 mL (0.68 mmol) of the 0.2 M 2-(4-heptylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 15 was added, and the mixture was stirred at 0°C for 20 minutes and at room temperature for 16 hours to prepare a zinc reagent solution. Separately, a 100 mL Schlenk flask was charged with 31.4 mg (0.0701 mmol) of 2,8-dibromoanthra[1,2-b:5,6-b']dithiophene (Compound 20) synthesized in Synthesis Example 23, 5.20 mg (0.00711 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 3 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade). The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 90 minutes and then at 50°C for 1 hour. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting solid was rinsed with methanol. The residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 5 / 1). The solid was rinsed with methanol and purified by recrystallization from hexane / toluene = 5 / 4 to obtain 3.5 mg of a yellow solid, 2,8-di(2-(4-n-heptylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 12) (yield: 7%). 1 H NMR(CDCl3):δ=8.59(s,2H),7.85(d,J=9.0Hz,2H),7.69(d,J=8.8Hz,2H),7.19(d,J=7.9Hz,2H),7.15(s,2H),7.13(d,J=8.0H) z,2H),3.32(t,J=7.6Hz,4H),3.11(t,J=8.5Hz,4H),2.59(t,J=7.6Hz,4H),1.61(m,4H),1.29(m,16H),0.89(t,J=6.5Hz,6H). (Compound 12) [ka]

[0164] Example 15 Synthesis of 2-(2-(4-normal-heptylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 18) (Step C2) Another component obtained by silica gel column chromatography in Example 14 was purified by recrystallization from hexane to obtain 3.5 mg of a yellow solid, 2-(2-(4-normal heptylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 18) (yield: 10%). 1 H NMR(CDCl3):δ=8.70(s,1H),8.62(s,1H),7.90(d,J=8.5Hz,1H),7.88(d,J=8.0Hz,1H),7 .82(d,J=8.9Hz,1H),7.71(d,J=8.9Hz,1H),7.54(d,J=5.4Hz,1H),7.49(d,J=5.1Hz,1H) ,7.19(d,J=8.0Hz,2H),7.16(s,1H),7.13(d,J=8.2Hz,2H),3.32(t,J=7.7Hz,2H),3.12( t,J=8.4Hz,2H),2.59(t,J=7.5Hz,2H),1.61(m,4H),1.29(m,8H),0.89(t,J=6.8Hz,3H). (Compound 18) [ka]

[0165] Synthesis Example 24: Synthesis of bromodithienobiphenylene derivative (compound 21) (Step A3) Under a nitrogen atmosphere, 126 mg (0.476 mmol) of a dithienobiphenylene derivative (Compound 2 in JP 2018-174322 A) and 15 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 0.30 mL (0.480 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry) was added. The mixture was stirred at -78 °C for 15 minutes, followed by stirring at room temperature for 30 minutes. The mixture was then cooled to -78 °C, and 6 mL of a THF solution (Fujifilm Wako Pure Chemical Industries, dehydrated grade) of 186 mg (0.571 mmol) of 1,2-dibromotetrachloroethane was added. The mixture was then stirred while warming to room temperature. After cooling on ice, water was added to quench the reaction, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane) and purified by recrystallization from hexane to obtain 85.1 mg of a yellow solid of a bromodithienobiphenylene derivative (compound 21) (yield: 47%). 1 H NMR (CDCl3): δ=7.23(d,J=7.1Hz,1H),7.21(d,J=5.4Hz,1H),7.05(d,J=5.8Hz,2H),7.04(s,1H),6.71(d,J=7.5Hz,1H),6.67(d,J=7.3Hz,1H).

[0166] Example 16 Synthesis of 2-(2-phenylethyl)dithienobiphenylene (Compound 13) (Step C3) Under a nitrogen atmosphere, 118 mg (0.866 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 1.90 mL (0.760 mmol) of the 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and the mixture was stirred at 0°C for 30 minutes and then at room temperature for 14 hours to prepare a zinc reagent solution. Separately, a 50 mL Schlenk flask was charged with 36.2 mg (0.105 mmol) of the bromodithienobiphenylene derivative synthesized in Synthesis Example 24, 10.1 mg (0.0138 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade). The previously prepared zinc reagent solution was added dropwise using a Teflon® cannula and stirred at room temperature for 5 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane). The resulting solid was rinsed with methanol to obtain 15.1 mg of a yellow solid, 2-(2-phenylethyl)dithienobiphenylene (Compound 13) (yield: 39%). 1 H NMR(CDCl3):δ=7.30(m,2H),7.21-7.18(m,5H),7.04(d,J=5.6Hz,1H),7.01(d,J=7.5Hz,1H),6.71 (d,J=7.3Hz,1H),6.69(s,1H),6.66(d,J=7.3Hz,1H),3.12(t,J=6.4Hz,2H),3.03(t,J=6.4Hz,2H). Melting point: 161°C (Compound 13) [ka]

[0167] Synthesis Example 25: Synthesis of 1-(2-bromoethyl)-4-methylbenzene Under a nitrogen atmosphere, 5.36 g (39.3 mmol) of 2-(p-tolyl)ethanol (Tokyo Chemical Industry Co., Ltd.) and 80 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL two-neck flask. The solution was cooled on ice, and 4.00 mL (42.1 mmol) of phosphorus tribromide was added. The mixture was stirred for 30 minutes, followed by 21 hours at room temperature. The reaction solution was poured onto ice, neutralized with saturated aqueous sodium bicarbonate, and then dichloromethane was added to separate the phases. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 4.05 g of a colorless liquid, 1-(2-bromoethyl)-4-methylbenzene (52% yield). 1 H NMR (CDCl3): δ=7.15(d,J=8.2Hz,2H),7.11(d,J=8.2Hz,2H),3.56(t,J=7.7Hz,2H),3.14(t,J=7.7Hz,2H),2.35(s,3H).

[0168] Synthesis Example 26: Synthesis of 2-(4-methylphenyl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 228 mg (9.36 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 50 mL two-neck flask and stirred under vacuum for 1 hour. Under a nitrogen atmosphere, 20 mL of a solution of 1.60 g (8.02 mmol) of 1-(2-bromoethyl)-4-methylbenzene (synthesized in Synthesis Example 25) in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added and stirred at room temperature for 90 minutes. The solid was removed by filtration to obtain a 0.4 M solution of 2-(4-methylphenyl)ethyl magnesium bromide in THF.

[0169] Example 17 Synthesis of 2-(2-(4-methylphenyl)ethyl)dithienobiphenylene (Compound 14) (Step C3) Under a nitrogen atmosphere, 114 mg (0.836 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 1.80 mL (0.720 mmol) of the 0.4 M 2-(4-methylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 26 was added, and the mixture was stirred at 0°C for 15 minutes and then at room temperature for 14 hours to prepare a zinc reagent solution. Separately, 24.4 mg (0.0711 mmol) of the bromodithienobiphenylene derivative synthesized in Synthesis Example 24, 9.00 mg (0.0123 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane). The obtained solid was rinsed with methanol to obtain 4.9 mg of a yellow solid of 2-(2-(4-methylphenyl)ethyl)dithienobiphenylene (Compound 14) (yield: 18%). 1 H NMR(CDCl3):δ=7.20(d,J=8.3Hz,1H),7.19(d,J=5.4Hz,1H),7.04(d,J=5.5Hz,1H),7.01(d,J=7.4Hz,1H),6.71 (d,J=7.3Hz,1H),6.69(s,1H),6.66(d,J=7.4Hz,1H),3.09(t,J=7.0Hz,2H),2.99(t,J=7.8Hz,2H),2.33(s,3H). Melting point: 151°C (Compound 14) [ka]

[0170] Synthesis Example 27 Synthesis of 2-bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22) (Step A-4) Under a nitrogen atmosphere, 481 mg (1.66 mmol) of anthra[1,2-b:5,6-b']dithiophene (Compound 19) synthesized in Synthesis Example 22 and 57 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 1.05 mL (1.68 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry) was added and stirred at -78 °C for 2 hours. Also cooled to -78 °C, 24 mL of a THF solution (Fujifilm Wako Pure Chemical Industries, dehydrated grade) of 634 mg (1.95 mmol) of 1,2-dibromotetrachloroethane was added and stirred while warming to room temperature. After ice cooling, water was added to quench the reaction, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 1) and purified by recrystallization from toluene to obtain 372 mg of a yellow solid of 2-bromoanthra[1,2-b:5,6-b']dithiophene (compound 22) (yield 51%). 1 H NMR (CDCl3): δ=8.70(s,1H),8.56(s,1H),7.90-7.86(m,3H),7.71(d,J=8.7Hz,1H),7.57(d,J=5.0Hz,1H),7.50(d,J=5.4Hz,1H),7.48(s,1H).

[0171] Example 18 Synthesis of 2-(2-(4-methylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 16) (Step C4) Under a nitrogen atmosphere, 207 mg (1.51 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 2.50 mL (1.00 mmol) of the 0.4 M 2-(4-methylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 26 was added, and the mixture was stirred at 0°C for 30 minutes and then at room temperature for 14 hours to prepare a zinc reagent solution. Separately, a 50 mL Schlenk flask was charged with 50.1 mg (0.136 mmol) of 2-bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22) synthesized in Synthesis Example 27, 11.0 mg (0.0150 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade). The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent; hexane:toluene = 1 / 0 to 10 / 1). The resulting solid was purified by recrystallization from hexane / toluene=5 / 1 to obtain 13.8 mg of a yellow solid of 2-(2-(4-methylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 16) (yield 30%). 1 H NMR(CDCl3):δ=8.70(s,1H),8.62(s,1H),7.90(d,J=8.8Hz,1H),7.87(d,J=8.8Hz,1H),7.82(d,J=8.7Hz,1H),7.71(d,J=8.8Hz, 1H),7.54(d,J=5.4Hz,1H),7.49(d,J=5.1Hz,1H),7.18-7.12(m,5H),3.32(t,J=7.7Hz,2H),3.12(t,J=7.4Hz,2H),2.35(s,3H). Melting point: 190℃ (Compound 16) [ka]

[0172] Synthesis Example 28: Synthesis of 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene (Step D1) Under a nitrogen atmosphere, 260 mg (0.591 mmol) of 2,6-difluoro-1,5-diiodobiphenylene synthesized using the method described in JP 2018-174322 A, 10.3 mg (0.0146 mmol) of bis(triphenylphosphine)dichloropalladium (Fujifilm Wako Pure Chemical Industries, Ltd.), 5.2 mg (0.0273 mmol) of copper(I) iodide (Fujifilm Wako Pure Chemical Industries, Ltd.), 6 mL of toluene, and 6 mL of triethylamine were added to a 50 mL Schlenk reaction vessel. 174 mg (1.77 mmol) of trimethylsilylacetylene (Tokyo Chemical Industry Co., Ltd.) was added to the resulting mixture and stirred at 30 °C for 6 hours. Water was added to the resulting reaction mixture to quench the reaction. The mixture was extracted with toluene, and the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene=1 / 0 to 20 / 1) to obtain 188 mg of the target pale yellow solid (yield 84%). 1 H NMR (CDCl3): δ=6.57(dd,J=7.3Hz,4.0Hz,2H),6.42(dd,J=11.0Hz,7.4Hz,2H),0.26(s,18H).

[0173] Synthesis Example 29: Synthesis of biphenyleno[2,1-b:6,5-b']dithiophene (Step E1) Under a nitrogen atmosphere, 133 mg (0.349 mmol) of 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene (synthesized in Synthesis Example 28), 301 mg (1.25 mmol) of sodium sulfide nonahydrate (Sigma-Aldrich), and 8 mL of DMSO (Fujifilm Wako Pure Chemical Industries) were added to a 100 mL Schlenk reaction vessel. The mixture was heated to 90 °C and stirred for 4 hours. The resulting reaction mixture was cooled to 0 °C, and water and toluene were added. After extraction with hot toluene and phase separation, the organic phase was washed with water. The organic phase was concentrated under reduced pressure to obtain 78 mg of a yellow solid, biphenyleno[2,1-b:6,5-b']dithiophene (84% yield). 1 H NMR (CDCl3): δ=7.31(d,J=5.7Hz,2H),7.18(d,J=7.6H),6.94(d,J=5.6Hz,2H),6.65(d,J=7.4,2H).

[0174] Synthesis Example 30: Synthesis of 2,7-dibromobiphenyleno[2,1-b:6,5-b']dithiophene (Step F1) Under a nitrogen atmosphere, 105 mg (0.397 mmol) of biphenyleno[2,1-b:6,5-b']dithiophene synthesized in Synthesis Example 29 and 9 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 0.94 mL (1.50 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry) was added and stirred at -78 °C for 10 minutes. After stirring at 20 °C for 25 minutes, 3 mL of a THF solution (Fujifilm Wako Pure Chemical Industries, dehydrated grade) of 555 mg (1.70 mmol) of 1,2-dibromotetrachloroethane was added at -78 °C and stirred while warming to room temperature. After ice cooling, water was added to quench the reaction. Hexane was added to the precipitated solid, and the solid was filtered using filter paper. The solid was washed with water, methanol, and hexane, and the resulting residue was dried to obtain 86 mg of a reddish-orange solid of 2,7-dibromobiphenyleno[2,1-b:6,5-b']dithiophene (yield 51%). 1 H NMR (CDCl3, 58°C): δ=7.02(d,J=7.7Hz,2H),6.96(s,2H),δ=6.58(d,J=7.7Hz,2H).

[0175] Example 19 Synthesis of 2,7-di(2-phenylethyl)dithienobiphenylene (Compound 9) (Step G1) Under a nitrogen atmosphere, 150 mg (1.10 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 1.4 mL (0.56 mmol) of 0.4 M 2-phenylethylmagnesium bromide / THF solution (synthesized in Synthesis Example 2) was added and stirred at room temperature for 1 hour to prepare a zinc reagent solution. To this solution, 45.4 mg (0.107 mmol) of 2,7-dibromobiphenyleno[2,1-b:6,5-b']dithiophene (synthesized in Synthesis Example 30) and 3.30 mg (0.00451 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich) were added. The mixture was stirred at 40 °C for 13 hours. The reaction mixture was cooled with ice, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 3 / 1). The resulting solid was purified by recrystallization from heptane / toluene = 1 / 2, yielding 26 mg of a yellow solid aromatic compound (Compound 9) (yield 51%). 1 H NMR (CDCl3): δ=7.34-7.20(m,10H),7.04(d,J=7.6Hz,2H),6.61(s,2H),6.63(d,J=7.4Hz,2H),δ=3.11(t,J=8.64Hz,4H),δ=3.03(t,J=8.4Hz,4H). (Compound 9) [ka]

[0176] Example 20 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 0.44 mg of 2,7-di(2-(4-propylphenyl)ethyl)dithienobiphenylene (compound 4) synthesized in Example 5 was used. The solution state was maintained even after 10 hours at 25°C (compound 4 concentration was 0.10 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0177] Example 21 (Fabrication of organic semiconductor layer and organic thin film transistor) Using the organic semiconductor layer-forming solution obtained in Example 20 and the materials and film-forming method for each component shown in Example 3, a bottom gate-bottom contact type p-type organic thin film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 1.86 cm 2 / V·sec, current on / off ratio is 1.1×10 6 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing at 130°C for 10 minutes. The carrier mobility of the hole was 1.70 cm 2 / V·sec, current on / off ratio is 1.0×10 6 Almost no deterioration in performance due to heat treatment was observed.

[0178] Example 22 (Fabrication of organic semiconductor layer and organic thin film transistor) In air, 0.87 mg of 2,7-di(2-(4-propylphenyl)ethyl)dithienobiphenylene (Compound 4) synthesized in Example 5 and 440 mg of anisole (Sigma-Aldrich) were added to a 10 ml sample tube, and the tube was heated at 60°C to prepare a 0.20 wt% solution of Compound 4. Using the obtained solution and the materials and film-forming method for each component shown in Example 3, a bottom-gate / bottom-contact type p-type organic thin-film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 2.48 cm 2 / V·sec, current on / off ratio is 1.6×10 6 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing at 130°C for 10 minutes. The carrier mobility of the hole was 2.40 cm 2 / V·sec, current on / off ratio is 1.4×10 6 Almost no deterioration in performance due to heat treatment was observed.

[0179] Example 23 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 1.74 mg of 2,7-di(2-(4-butylphenyl)ethyl)dithienobiphenylene (compound 5) synthesized in Example 6 was used. The solution state was maintained even after 10 hours at 25°C (compound 5 concentration was 0.40 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0180] Example 24 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 0.87 mg of 2,7-di(2-(4-heptylphenyl)ethyl)dithienobiphenylene (compound 6) synthesized in Example 7 was used. The solution state was maintained even after 10 hours at 25°C (compound 6 concentration was 0.20 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0181] Example 25 (Fabrication of organic semiconductor layer and organic thin film transistor) Using the organic semiconductor layer-forming solution obtained in Example 24 and the materials and film-forming method for each component shown in Example 3, a bottom-gate-bottom-contact type p-type organic thin-film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 1.19 cm 2 / V·sec, current on / off ratio is 1.1×10 6 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing at 130°C for 10 minutes. The carrier mobility of the hole was 1.15 cm 2 / V·sec, current on / off ratio is 1.0×10 6 Almost no deterioration in performance due to heat treatment was observed.

[0182] Example 26 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 0.87 mg of 2,8-di(2-phenylethyl)anthra[1,2-b:5,6-b']dithiophene (compound 10) synthesized in Example 10 was used. The solution state was maintained even after 10 hours at 25°C (compound 10 concentration was 0.20 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0183] Example 27 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 4.35 mg of 2-(2-phenylethyl)dithienobiphenylene (compound 13) synthesized in Example 16 was used. The solution state was maintained even after 10 hours at 25°C (compound 13 concentration was 1.00 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0184] Example 28 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 4.35 mg of 2-(2-(4-methylphenyl)ethyl)dithienobiphenylene (compound 14) synthesized in Example 17 was used. The solution state was maintained even after 10 hours at 25°C (compound 14 concentration was 1.00 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0185] Example 29 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 1.74 mg of 2-(2-phenylethyl)anthra[1,2-b:5,6-b']dithiophene (compound 15) synthesized in Example 11 was used. The solution state was maintained even after 10 hours at 25°C (compound 15 concentration was 0.40 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0186] Example 30 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 2.18 mg of 2-(2-(4-methylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (compound 16) synthesized in Example 18 was used. The solution state was maintained even after 10 hours at 25°C (compound 16 concentration was 0.50 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0187] Example 31 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 4.35 mg of 2-(2-(4-normal butylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (compound 17) synthesized in Example 13 was used. The solution state was maintained even after 10 hours at 25°C (compound 17 concentration was 1.00 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0188] Example 32 (Fabrication of organic semiconductor layer and organic thin film transistor) An organic semiconductor layer-forming solution was prepared in the same manner as in Example 2, except that 0.87 mg of 2-(2-(4-normal butylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (compound 17) synthesized in Example 13 was used (the concentration of compound 17 was 0.20 wt %). Using the obtained organic semiconductor layer-forming solution and the materials and film-forming method for each component shown in Example 3, a bottom-gate-bottom-contact type p-type organic thin-film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 1.13 cm 2 / V·sec, current on / off ratio is 8.1×10 7 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing at 130°C for 10 minutes. The carrier mobility of the hole was 1.10 cm 2 / V·sec, current on / off ratio is 8.0×10 7 Almost no deterioration in performance due to heat treatment was observed.

[0189] Example 33 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 0.87 mg of 2-(2-(4-normal heptylphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (compound 18) synthesized in Example 15 was used. The solution state was maintained even after 10 hours at 25°C (compound 18 concentration: 0.20 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0190] Synthesis Example 31: Synthesis of 4-propoxybenzeneethanol Under a nitrogen atmosphere, 4.51 g (21.0 mmol) of 1-bromo-4-propoxybenzene (Tokyo Chemical Industry Co., Ltd.) and 80 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, and 22.0 mL (35.0 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at -78 °C for 2 hours. 25.0 mL (30.0 mmol) of 1.2 M ethylene oxide in THF (Tokyo Chemical Industry Co., Ltd.) was added at -78 °C and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, followed by the addition of diethyl ether to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane, ethyl acetate) to obtain 2.83 g of a colorless liquid, 4-propoxybenzeneethanol (yield: 64%). 1 H NMR(CDCl3):δ=7.13(dd,J=1.9Hz,6.4Hz,2H),6.85(dd,J=2.1Hz,6.4Hz,2H),3.91(t,J=6.7Hz,2H) ,3.82(t,J=6.7Hz,2H),2.81(t,J=6.6Hz,2H),1.81(tq,J=6.6Hz,7.4Hz,2H),1.04(t,J=7.4Hz,3H).

[0191] Synthesis Example 32: Synthesis of 1-(2-bromoethyl)-4-propoxybenzene Under a nitrogen atmosphere, 2.83 g (15.7 mmol) of 4-propoxybenzeneethanol synthesized in Synthesis Example 31 and 20 ml of toluene (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 100 ml recovery flask. 0.80 ml (8.4 mmol) of phosphorus tribromide was added and the mixture was stirred at room temperature for 20 minutes, followed by stirring at 100°C for 4 hours. The reaction solution was poured onto ice, neutralized with saturated aqueous sodium bicarbonate, and then dichloromethane was added to separate the phases. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 3.40 g of a colorless liquid, 1-(2-bromoethyl)-4-propoxybenzene (yield: 84%). 1 H NMR(CDCl3):δ=7.11(d,J=8.4Hz,2H),6.86(d,J=8.6Hz,2H),3.91(t,J=6.6Hz,2H),3.53(t ,J=7.4Hz,2H),3.10(t,J=7.6Hz,2H),1.82(tq,J=6.8Hz,7.4Hz,2H),1.04(t,J=7.4Hz,3H).

[0192] Synthesis Example 33 Synthesis of 2-(4-propoxyphenyl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 172 mg (7.06 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 20 mL two-neck flask and stirred under vacuum for 1 hour. Under a nitrogen atmosphere, 15 mL of a solution of 1.46 g (6.00 mmol) of 1-(2-bromoethyl)-4-propoxybenzene (synthesized in Synthesis Example 32) in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added and stirred at room temperature for 1 hour. The solid was removed by filtration to obtain a 0.4 M solution of 2-(4-propoxyphenyl)ethyl magnesium bromide in THF.

[0193] Example 34 Synthesis of 2-(2-(4-propoxyphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 23) (Step C4) Under a nitrogen atmosphere, 149 mg (1.10 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 1.80 mL (0.72 mmol) of the 0.4 M 2-(4-propoxyphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 33 was added, and the mixture was stirred at 0°C for 15 minutes and then at room temperature for 15 hours to prepare a zinc reagent solution. Separately, 50.6 mg (0.144 mmol) of 2-bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22) synthesized in Synthesis Example 27, 6.6 mg (0.0090 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 5). The obtained solid was purified by recrystallization from hexane / toluene=10 / 3 to obtain 8.5 mg of a yellow solid of 2-(2-(4-propoxyphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 23) (yield 13%). 1 H NMR(CDCl3):δ=8.69(s,1H),8.62(s,1H),7.90(d,J=9.1Hz,1H),7.87(d,J=9.2Hz,1H),7. 82(d,J=8.9Hz,1H),7.71(d,J=8.8Hz,1H),7.54(d,J=5.0Hz,1H),7.49(d,J=5.1Hz,1H),7 .17(d,J=8.6Hz,1H),7.14(s,1H),6.86(d,J=8.7Hz,1H),3.92(t,J=6.4Hz,2H),3.30(t,J =7.6Hz,2H),3.10(t,J=7.5Hz,2H),1.81(tq,J=7.5Hz,7.6Hz,2H),1.04(t,J=7.5Hz,3H). Melting point: 181°C (Compound 23) [ka]

[0194] Synthesis Example 34: Synthesis of 2-(4-methoxyphenyl)ethylmagnesium bromide (Step B1) Under a nitrogen atmosphere, 161 mg (6.61 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, shavings) was added to a 20 mL two-neck flask and stirred under vacuum for 1 hour. Under a nitrogen atmosphere, 15 mL of a solution of 1.29 g (6.00 mmol) of 4-methoxyphenethyl bromide (Sigma-Aldrich) in THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) was added and stirred at room temperature for 1 hour. The solid was removed by filtration to obtain a 0.4 M solution of 2-(4-methoxyphenyl)ethyl magnesium bromide in THF.

[0195] Example 35 Synthesis of 2-(2-(4-methoxyphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 24) (Step C4) Under a nitrogen atmosphere, 125 mg (0.914 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice cooling. Under ice cooling, 1.60 mL (0.640 mmol) of the 0.4 M 2-(4-methoxyphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 34 was added, and the mixture was stirred at 0°C for 15 minutes and then at room temperature for 15 hours to prepare a zinc reagent solution. Separately, 50.4 mg (0.136 mmol) of 2-bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22) synthesized in Synthesis Example 27, 7.8 mg (0.011 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 50 mL Schlenk flask. The previously prepared zinc reagent solution was added dropwise using a Teflon cannula and stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, and 1 M hydrochloric acid was added, followed by the addition of toluene to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 5). The resulting solid was purified by recrystallization from hexane / toluene=3 / 2 to obtain 17.8 mg of a yellow solid of 2-(2-(4-methoxyphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 24) (yield 31%). 1 H NMR(CDCl3):δ=8.70(s,1H),8.62(s,1H),7.90(d,J=9.2Hz,1H),7.87(d,J=9.2Hz,1H),7.82(d,J=8.7Hz,1H),7.71(d,J=8.7Hz,1H),7.54(d,J=5.3 Hz,1H),7.49(d,J=5.1Hz,1H),7.18(d,J=8.6Hz,1H),7.14(s,1H),6.86(d ,J=8.6Hz,1H),3.81(s,3H),3.30(t,J=7.5Hz,2H),3.09(t,J=7.5Hz,2H). Melting point: 231°C (Compound 24) [ka]

[0196] Example 36 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 4.35 mg of 2-(2-(4-propoxyphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (compound 23) synthesized in Example 34 was used. The solution state was maintained even after 10 hours at 25°C (compound 23 concentration was 1.00 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0197] Example 37 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2, except that 0.44 mg of 2-(2-(4-methoxyphenyl)ethyl)anthra[1,2-b:5,6-b']dithiophene (compound 24) synthesized in Example 35 was used. The solution state was maintained even after 10 hours at 25°C (compound 24 concentration was 0.10 wt%), confirming that the compound is suitable for film formation by drop casting and inkjet.

[0198] Comparative Example 1 (Preparation of solution for forming organic semiconductor layer) In air, 0.44 mg of 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (Sigma-Aldrich) and 434 mg of toluene (Fujifilm Wako Pure Chemical Industries, Pure Grade) were added to a 10 ml sample tube, heated to 50°C, and allowed to cool to room temperature (25°C). A solid was confirmed to have precipitated, confirming that the compound is unsuitable for film formation by drop casting or inkjet due to its low solubility.

[0199] Comparative Example 2 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in a 10 ml sample tube under air using 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (Sigma-Aldrich) in the same manner as in Example 2. The solution remained in solution (0.20 wt %) even after 10 hours at 25°C, confirming that the compound is suitable for film formation by drop casting and inkjet.

[0200] (Fabrication of organic semiconductor layers and organic thin film transistors) Using the organic semiconductor layer-forming solution, a thin film of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene was prepared in the same manner as in Example 4, and a bottom-gate-bottom-contact type p-type organic thin-film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 1.02 cm 2 / V·sec, current on / off ratio is 3.0×10 5 It was. Furthermore, the electrical properties of this organic thin-film transistor were measured after annealing it at 130°C for 10 minutes. As a result, transistor operation was not obtained, and a significant performance degradation due to the heat treatment was observed. Microscopic observation confirmed that the organic semiconductor layer had been destroyed by the heat.

[0201] Comparative Example 3 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in a 10 ml sample tube under air using 2,7-di(normal octyl)dithienobiphenylene (compound 3 in JP 2018-174322 A) in the same manner as in Example 2. The solution remained in solution (0.20 wt %) even after 10 hours at 25°C, confirming that the compound is suitable for film formation by drop casting and inkjet.

[0202] (Fabrication of organic semiconductor layers and organic thin film transistors) Using the organic semiconductor layer-forming solution and the materials and film-forming method for each component shown in Example 3, a top-gate-bottom-contact type p-type organic thin-film transistor was fabricated. The transfer characteristics of the transistor element were evaluated, and the carrier mobility of the holes was found to be 0.60 cm 2 / V·sec, current on / off ratio is 3.0×10 6 This is what happened.

[0203] Comparative Example 4 (Preparation of solution for forming organic semiconductor layer) A solution for forming an organic semiconductor layer was prepared in a 10 ml sample tube under air using 2,8-dioctylanthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 6 in the same manner as in Example 2. The solution remained in solution state (0.20 wt %) even after 10 hours at 25°C, confirming that the compound is suitable for film formation by drop casting and inkjet.

[0204] (Fabrication of organic semiconductor layers and organic thin film transistors) This organic semiconductor layer-forming solution was used, and the materials and film-forming method for each component were used as shown in Example 3. However, no thin film was formed, and a top-gate-bottom-contact type p-type organic thin-film transistor could not be fabricated. [Industrial Applicability]

[0205] The aromatic compound of the present invention provides high carrier mobility and is excellent in heat resistance and solubility, and is therefore expected to be used as a material for semiconductor devices such as organic thin film transistors. [Explanation of symbols]

[0206] (A): Bottom-gate / top-contact organic thin-film transistor (B): Bottom-gate / bottom-contact organic thin-film transistor (C): Top-gate-top-contact organic thin-film transistor (D): Top-gate / bottom-contact organic thin-film transistor 1: Organic semiconductor layer 2: Circuit board 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims

1. An aromatic compound represented by any one of the following formulas (7-1), (7-2), (7-4) and (7-5): 【Chemistry 1】 (where X ８ , X ９ are each independently an oxygen atom, a sulfur atom, a selenium atom, or NR ４４ Indicates Y ５ , Y ６ are each independently CR ４５ or a nitrogen atom. ３８ ~R ４５ , R ７１ , R ７２ each independently represents one of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, or a group represented by the following formula (2), and R ３８ and R ４１ At least one of the above is a group represented by the following formula (2): 【Chemistry 2】 (wherein A represents one member of the group consisting of a phenyl group, an alkyl-substituted phenyl group having 4 to 26 carbon atoms, an alkyloxy-substituted phenyl group having 4 to 26 carbon atoms, a fluorine-substituted phenyl group having 4 to 26 carbon atoms, a 2-furyl group, a 2-thienyl group, and an alkyl-substituted heteroaryl group having 4 to 24 carbon atoms; l and n each independently represent 0 or 1, and m represents an integer of 1 to 20. Z １ , Z ２ and each occurrence may be the same or different and represent one of the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms.

2. The aromatic compound according to claim 1, which is a compound represented by the formula (7-1), the formula (7-2), or the formula (7-5).

3. R ３８ and R ４１ are each independently one of the group consisting of the group represented by formula (2), a hydrogen atom, and a fluorine atom, and R ３９ , R ４０ , R ４２ ~R ４５ , R ７１ , R ７２ The aromatic compound according to claim 1 or 2, wherein is a hydrogen atom.

4. R ３８ and R ４１ is a group represented by the formula (2), and R ３９ , R ４０ , R ４２ ~R ４５ , R ７１ , R ７２ The aromatic compound according to claim 1 or 2, wherein is a hydrogen atom.

5. A solution for forming an organic semiconductor layer, comprising the aromatic compound according to any one of claims 1 to 4.

6. An organic semiconductor layer containing the aromatic compound according to any one of claims 1 to 4.

7. An organic thin film transistor comprising the organic semiconductor layer according to claim 6.

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