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

Abstract

To provide an aromatic compound containing a specific substituent which is a coating-type organic semiconductor material having high carrier mobility, high heat resistance and high solubility and to provide an organic semiconductor layer and an organic thin-film transistor using the same.SOLUTION: Specifically, there is provided, for example. the following compound 1.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel aromatic compound that can be applied to electronic materials such as organic semiconductor materials, an organic semiconductor layer using the same, and an organic thin film transistor. In particular, since it has excellent solubility and heat resistance, it relates to an aromatic compound having specific substituents applicable to various device manufacturing processes, an organic semiconductor layer using the same, and an organic thin film transistor.

Background Art

[0002] Organic semiconductor devices typified by organic thin film transistors have attracted attention in recent years because they have characteristics that inorganic semiconductor devices do not have, such as energy saving, low cost, and flexibility. This organic semiconductor device is composed of several types of materials such as an organic semiconductor layer, a substrate, an insulating layer, and electrodes. Among them, the organic semiconductor layer that is responsible for charge carrier movement plays a central role in the device. And since the performance of the organic semiconductor device depends on the carrier mobility of the organic semiconductor material that constitutes this organic semiconductor layer, the emergence of an organic semiconductor material that gives high carrier mobility is desired.

[0003] As methods for fabricating an organic semiconductor layer, methods such as a vacuum evaporation method in which an organic material is vaporized under high-temperature vacuum and a coating method in which an organic material is dissolved in an appropriate solvent and the solution is applied are generally known. Among these, in the coating method, since it can be carried out using printing technology without using high-temperature and high-vacuum conditions, it is expected to significantly reduce the manufacturing cost of device fabrication, and it is an economically preferable process.

[0004] The organic semiconductor materials used in such coating methods preferably have a heat resistance of 130°C or higher and a solubility at room temperature of 0.1% by weight or more from the viewpoints of high carrier mobility and the process of device fabrication. Further, in the case of a transistor used for electronic paper applications, the carrier mobility is preferably 0.1 cm 2 / V·sec or more, and the threshold voltage is preferably -3V to +3V.

[0005] Here, generally, small-molecule semiconductors having a rod-shaped molecular major axis of a condensed ring system are known to exhibit high carrier mobility because they have higher crystallinity than polymer semiconductors. However, generally, small-molecule semiconductors have a problem of low solubility, and semiconductors with an alkyl group introduced to improve solubility have been reported, but there is a problem that the carrier mobility and heat resistance decrease. Also, semiconductors with an aromatic substituent introduced for the purpose of expressing high carrier mobility by π-stacking have been reported, but it has been reported that the solubility significantly decreases in exchange for the expression of high mobility. Therefore, at present, almost no small-molecule organic semiconductor materials having both high carrier mobility, high heat resistance, and high solubility are known.

[0006] Currently, as small-molecule materials, 2,7-dialkyl-substituted benzothieno[3,2-b]benzothiophene (see, for example, Patent Document 1 and Non-Patent Document 1), 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (see, for example, Non-Patent Document 2), dithienobiphenylene derivatives, etc. have been proposed.

[0007] However, in the case of the dialkyl-substituted benzothieno[3,2-b]benzothiophene described in Patent Document 1 and Non-Patent Document 1, there was a problem of heat resistance that the transistor operation was lost when heated to 130 °C or higher.

[0008] The 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene described in Non-Patent Document 2 was generally hardly soluble in organic solvents and had a problem in solubility.

[0009] Although Patent Document 2 proposes an aromatic compound with high mobility, there is a problem with the threshold voltage.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Non-Patent Document

[0011]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0012] The present invention has been made in view of the above problems, and an object thereof is to provide a novel coating-type organic semiconductor material having high carrier mobility, low threshold voltage, high heat resistance, and high solubility.

Means for Solving the Problems

[0013] As a result of intensive studies to solve the above problems, the present inventor has found that a novel aromatic compound having a specific substituent gives high carrier mobility and a low threshold voltage, and also becomes an organic semiconductor material having high heat resistance and high solubility, thereby completing the present invention.

[0014] That is, the present invention relates to an aromatic compound represented by any one of the following formulas (1-I) or (1-II), an organic semiconductor layer containing the aromatic compound, and an organic thin film transistor including the organic semiconductor layer.

[0015]

Chemical Formula

[0016] [(Here, X 1 , X 2 each independently represents an oxygen atom, a sulfur atom, a selenium atom, or NR 9 . Y1 , Y 2 each independently represents CR 10 or a nitrogen atom. R 2 ~R 4 , R 6 ~R 10 each independently represents 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 R 5 represents a linear alkyl group having 1 to 20 carbon atoms, and R 1 is a group represented by the following formula (2).)

[0017] [Chemical formula]

[0018] (Here, l and m each independently represent 0 or 1, and n represents an integer of 1 to 20. R 11 ~R 15 each independently represents 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 at least one of R 11 ~R 15 is a linear alkyl group having 1 to 20 carbon atoms.)] [Advantages of the Invention]

[0019] The novel aromatic compound of the present invention provides high carrier mobility, low threshold voltage, high heat resistance, and high solubility. Therefore, it is possible to provide an organic thin-film transistor that exhibits excellent semiconductor characteristics by coating, and the effect is extremely high. [Brief Description of the Drawings]

[0020]

Figure 1

Mode for Carrying Out the Invention

[0021] The present invention will be described in detail below.

[0022] The present invention is an aromatic compound represented by any one of the above formulas (1-I) or (1-II) (hereinafter referred to as "the compound of the present invention"). Since it has a high carrier mobility, the present invention is preferably represented by the above formula (1-I), and X in the formula (1-I) 1 , X 2 is a sulfur atom, Y 1 , Y 2 is CH, l and m in the formula (2) are each 0, and R 2 to R 4 , R 6 to R 12 , R 14 , R 15 is a hydrogen atom, and the aromatic compound (1-a) is particularly preferred..

[0023]

Chemical formula

[0024] (Here, R 5 has the same meaning as R 5 represented by the formula (1-I), and n, R 13 has the same meaning as n, R 13 represented by the formula (2).) X in the formulas (1-I) and (1-II) 1 , X 2 each independently represents one kind of the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and NR 9 . In order for the compound of the present invention to exhibit higher stability, at least one of X 1 and X 2 is preferably either a sulfur atom or a selenium atom, and more preferably both are sulfur atoms.

[0025] Y in the formulas (1-I) and (1-II) 1 , Y2 each independently represents either CR 10 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 them is preferably CR 10 and more preferably both are CR 10 .

[0026] R 2 ~R 4 , R 6 ~R 10 in formula (1-I) and formula (1-II) each independently represents one member selected from 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, and a group represented by an aryl group having 4 to 26 carbon atoms; R 5 represents a linear alkyl group having 1 to 20 carbon atoms; and R 1 represents a group represented by formula (2).

[0027] Examples of the halogen atom in the R 2 ~R 4 , R 6 ~R 10 include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Since the compound of the present invention is stable, either a fluorine atom or a chlorine atom is preferred.

[0028] The R 2 ~R 4 , R 6 ~R 10Examples of the alkyl group having 1 to 20 carbon atoms include linear, branched, or cyclic alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isovaleryl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. Among them, since the compound of the present invention is particularly an aromatic compound showing high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferable, and a linear alkyl group having 1 to 14 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group is more preferable.

[0029] The R 2 ~R 4 、R 6 ~R 10 Examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl group, propenyl group, butenyl group, 2-methylpropenyl group, n-pentenyl group, 2-methylbutenyl group, n-hexenyl group, 2-methylpentenyl group, n-heptenyl group, n-octenyl group, 2-ethylhexenyl group, n-nonel group, 2-ethylheptenyl group, n-decenyl group, n-dodecenyl group, cyclopentenyl-1-group, cyclohexenyl-1-group, cycloheptenyl-1-group, etc.

[0030] The R 2 ~R 4 、R 6 ~R 10 Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, propynyl group, butynyl group, n-pentynyl group, n-hexynyl group, n-heptynyl group, n-octynyl group, n-nonynyl group, n-decynyl group, n-dodecynyl group, etc.

[0031] The R 2 ~R 4 、R 6 ~R 10 Examples of the C4-C22 alkadienyl group in R~R, R~R 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, an n-tridecadienyl group, etc. It is preferably a C4-C22 alk-1,3-dienyl group, more preferably 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.

[0032] The R 2 ~R 4 、R 6 ~R 10 Examples of the C4-C22 alkadiynyl group in R~R, R~R 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, etc. It is preferably a C4-C22 1,3-alkadiynyl group, more preferably 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.

[0033] The R 2 ~R 4 、R 6 ~R 10The aryl group having 4 to 26 carbon atoms in [compound] 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; an alkyl-substituted phenyl group 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 and a 2-thienyl group; an alkyl-substituted heteroaryl group such as 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, 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.

[0034] The R 5 Examples of the straight-chain alkyl group having 1 to 20 carbon atoms in [compound] include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, and an n-octadecyl group. Among them, since the compound of the present invention becomes an aromatic compound showing high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferable, a straight-chain alkyl group having 1 to 14 carbon atoms which is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, or an n-tetradecyl group is more preferable, and a straight-chain alkyl group having 4 to 8 carbon atoms which is an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or an n-octyl group is even more preferable.

[0035] These Rs 2 ~R 4 、R 6 ~R 10 are preferably one kind of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 4 to 26 carbon atoms for the stability of the compound of the present invention, and are more preferably either a hydrogen atom or a group represented by an alkyl group having 1 to 20 carbon atoms for the high solubility of the compound of the present invention, and are even more preferably a hydrogen atom from the viewpoint of high carrier mobility of the compound of the present invention.

[0036] In formula (2), l and m each independently represent 0 or 1. Preferably, m is 0 for the ease of synthesis of the compound of the present invention, and more preferably, both l and m are 0 for the high carrier mobility of the compound of the present invention.

[0037] In formula (2), n represents an integer of 1 to 20. Preferably, n is an integer of 1 to 3 for the high solubility of the compound of the present invention, more preferably, n is an integer of 1 to 2 for the high heat resistance of the compound of the present invention, and even more preferably, n is 2 for the high carrier mobility of the compound of the present invention.

[0038] Rs in formula (2) 11 ~R 15 each independently represent one kind 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, and an aryl group having 4 to 26 carbon atoms, and at least one of Rs 11 ~R 15 represents a linear alkyl group having 1 to 20 carbon atoms.

[0039] The Rs 11 ~R 15Examples of the alkyl group having 1 to 20 carbon atoms include linear, branched, or cyclic alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isovaleryl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. Among them, since the compound of the present invention becomes an aromatic compound showing high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferable, and a linear alkyl group having 1 to 14 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group is more preferable.

[0040] The R 11 ~R 15 Examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl group, propenyl group, butenyl group, 2-methylpropenyl group, n-pentenyl group, 2-methylbutenyl group, n-hexenyl group, 2-methylpentenyl group, n-heptenyl group, n-octenyl group, 2-ethylhexenyl group, n-nonel group, 2-ethylheptenyl group, n-decenyl group, n-dodecenyl group, cyclopentenyl-1-group, cyclohexenyl-1-group, cycloheptenyl-1-group, etc.

[0041] The R 11 ~R 15 Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, propynyl group, butynyl group, n-pentynyl group, n-hexynyl group, n-heptynyl group, n-octynyl group, n-nonynyl group, n-decynyl group, n-dodecynyl group, etc.

[0042] The R 11 ~R 15Examples of the C4-22 alkadienyl group 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, an n-tridecadienyl group, etc., preferably a C4-22 alka-1,3-dienyl group, more preferably 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.

[0043] The R 11 ~R 15 Examples of the C4-22 alkadiynyl group 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, etc., preferably a C4-22 1,3-alkadiynyl group, more preferably 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.

[0044] The R 11 ~R 15The aryl group having 4 to 26 carbon atoms in [X] 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; an alkyl-substituted phenyl group 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 and a 2-thienyl group; an alkyl-substituted heteroaryl group such as 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, 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.

[0045] The R 11 ~R 15 It should be noted that the part "[X]" in the translation of is a placeholder in the original text and needs to be filled in according to the actual context.In this case, at least one of them is a linear alkyl group having 1 to 20 carbon atoms. Examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, and an n-octadecyl group. Among them, since the compound of the present invention particularly becomes an aromatic compound exhibiting high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferable, and a linear alkyl group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group is more preferable, and a linear alkyl group having 4 to 8 carbon atoms such as an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group is even more preferable.

[0046] In formula (2), it is preferable that both m and l are 0 and n is 2. Thereby, the compound of the present invention exhibits higher carrier mobility.

[0047] The group represented by formula (2) is preferably a 4-methylphenethyl group, a 4-ethylphenethyl group, a 4-propylphenethyl group, a 4-butylphenethyl group, a 4-pentylphenethyl group, a 4-hexylphenethyl group, a 4-heptylphenethyl group, a 4-octylphenethyl group, a 4-nonylphenethyl group, or a 4-decylphenethyl group in order for the compound of the present invention to have high carrier mobility, and is more preferably a 4-butylphenethyl group, a 4-pentylphenethyl group, a 4-hexylphenethyl group, a 4-heptylphenethyl group, or a 4-octylphenethyl group in order for the compound of the present invention to have high heat resistance, high solubility, and high carrier mobility.

[0048] These R 11 ~R 15Among them, it is preferably one kind of the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 4 to 26 carbon atoms for the stability of the compound of the present invention, and it is more preferably either a hydrogen atom or an alkyl group having 1 to 20 carbon atoms for the high solubility of the compound of the present invention. From the viewpoint of high carrier mobility of the compound of the present invention, R 13 is a linear alkyl group, and R 11 , R 12 , R 14 , R 15 are more preferably hydrogen atoms.

[0049] Specific examples of the compound of the present invention include the following,

[0050]

Chemical formula

[0051]

Chemical formula

[0052]

Chemical formula

[0053]

Chemical formula

[0054]

Chemical formula

[0055]

Chemical formula

[0056]

Chemical formula

[0057]

Chem.

[0058] Preferably

[0059]

Chem.

[0060]

Chem.

[0061]

Chem.

[0062]

Chem.

[0063] and particularly preferably, the following can be mentioned.

[0064]

Chem.

[0065]

Chem.

[0066] As a method for producing the compound of the present invention, any production method can be used as long as it is possible to produce the compound.

[0067] As a method for producing the aromatic compound of the present invention, for example, X of formula (1-I) 1 , X 2 is a sulfur atom, Y 1 , Y 2is CH, l and m in formula (2) are each 0, and R 2 ~R 4 、R 6 ~R 12 、R 14 、R 15 The aromatic compound (1-a) in which is a hydrogen atom can be produced by the method passing through the steps of A1 or B1 and C1, D1, C2 below, or the method passing through the steps of A1 or B1 and C3 below. (Step A1); A method for producing a boronic acid ester by reacting an alkyl bromide derivative with bis(pinacolato)diboron in the presence of a copper catalyst and a ligand. (Step B1); A method for producing a boronic acid ester by reacting an alkene with borane and water to form a boronic acid and then reacting it with pinacol. (Step C1); A method for producing an anthradithiophene derivative by reacting the boronic acid ester obtained in Step A1 or B1 with 2-bromoanthra[1,2-b:5,6-b']dithiophene in the presence of a base and a palladium catalyst. (Step D1); A method for synthesizing a monobromoanthradithiophene derivative by converting the anthradithiophene derivative obtained in Step C1 into a monolithium salt with n-butyllithium and then using a brominating agent. (Step C2); A method for producing the aromatic compound (1-a) by reacting a boronic acid with the monobromoanthradithiophene derivative obtained in Step D1 in the presence of a base and a palladium catalyst. (Step C3); A method for producing the aromatic compound (1-a) by reacting the boronic acid ester obtained in Step A1 or B1 with the monobromoanthradithiophene derivative in the presence of a base and a palladium catalyst.

[0068] The details of each step are shown below. (Step A1) The A1 step is a method for producing a boronic acid ester by reacting an alkyl bromide derivative with bis(pinacolato)diboron in the presence of a copper catalyst and a ligand.

[0069] Examples of the copper catalyst in this case include copper(I) iodide, copper(I) bromide, copper(I) chloride, etc. Examples of the ligand include Xantphos, Ruphos, Xphos, etc.

[0070] Examples of the alkyl bromide derivative in the A1 step include 1-(2-bromoethyl)-4-methylbenzene, 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, etc.

[0071] The conditions for preparing the boronic ester can be carried out in a solvent such as THF or diethyl ether in the temperature range of 0°C to 50°C. (Step B1) This B1 step is a method for producing a boronic acid ester by reacting an alkene with borane and water to form a boronic acid and then reacting it with pinacol.

[0072] The conditions for preparing the boronic acid can be carried out, for example, using 1 to 3 equivalents of borane in a solvent such as THF or diethyl ether in the temperature range of 0°C to 40°C.

[0073] Also, during the reaction with pinacol, magnesium sulfate, sodium sulfate, etc. can be added as a dehydrating agent.

[0074] Examples of the alkene in the B1 step include 4-n-methylstyrene, 4-n-ethylstyrene, 4-n-propylstyrene, 4-n-butylstyrene, 4-n-pentylstyrene, 4-n-hexylstyrene, 4-n-heptylstyrene, 4-n-octylstyrene, etc. (Step C1) The C1 process is a method for producing an anthradithiophene derivative by a Suzuki coupling reaction between a boronic acid ester obtained in the A1 or B1 process and 2-bromoanthra[1,2-b:5,6-b']dithiophene in the presence of a palladium catalyst.

[0075] This reaction can be carried out, for example, in a solvent such as toluene, N,N-dimethylformamide (hereinafter abbreviated as DMF), N,N-dimethylacetamide (hereinafter abbreviated as DMA), THF, etc., in a temperature range of 20°C to 100°C. Note that water may be added as a solvent.

[0076] Examples of the palladium catalyst in the C1 process include palladium acetate, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc., and Ruphos, Xantphos, Xphos, etc. can be added as ligands.

[0077] Examples of the base used in the C1 process include potassium tert-butoxide, sodium tert-butoxide, sodium hydroxide, potassium hydroxide, etc. (D1 process) The D1 process is a method for producing a monobromoanthradithiophene derivative by converting the anthradithiophene derivative obtained in the C1 process into a monolithium salt with 1 equivalent or more of n-butyllithium and reacting it with a brominating agent.

[0078] The conditions for preparing the monolithium salt can be carried out, for example, using 1.0 to 5.0 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether in a temperature range of -80°C to 30°C.

[0079] Examples of the brominating agent include carbon tetrabromide, 1,2-dibromotetrachloroethane, etc. (C2 process) The C2 process is a method for producing the aromatic compound (1-a) by a Suzuki coupling reaction between a boronic acid and the monobromoanthradithiophene derivative obtained in the D1 process in the presence of a palladium catalyst.

[0080] This reaction can be carried out, for example, in a solvent such as toluene, N,N-dimethylformamide (hereinafter abbreviated as DMF), N,N-dimethylacetamide (hereinafter abbreviated as DMA), THF, etc. in a temperature range of 20°C to 100°C. Note that water may be added as a solvent.

[0081] Examples of the palladium catalyst in the C2 process include palladium acetate, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc., and Ruphos, Xantphos, Xphos, etc. can be added as ligands.

[0082] Examples of the base used in the C2 process include potassium tert-butoxide, sodium tert-butoxide, sodium hydroxide, potassium hydroxide, etc.

[0083] Examples of the boronic acid used in the C2 process include methylboronic acid, ethylboronic acid, propylboronic acid, butylboronic acid, pentylboronic acid, hexylboronic acid, heptylboronic acid, octylboronic acid, nonylboronic acid, decylboronic acid, etc. (C3 process) The C3 process is a method for producing the aromatic compound (1-a) by a Suzuki coupling reaction between the boronic acid ester obtained in the A1 or B1 process and the monobromoanthradithiophene derivative in the presence of a palladium catalyst.

[0084] The reaction can be carried out in a solvent such as toluene, N,N-dimethylformamide (hereinafter abbreviated as DMF), N,N-dimethylacetamide (hereinafter abbreviated as DMA), THF, etc. in a temperature range of 20 °C to 100 °C. Water may be added as a solvent.

[0085] Examples of the palladium catalyst in the C3 step include palladium acetate, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc., and Ruphos, Xantphos, Xphos, etc. can be added as ligands.

[0086] Examples of the base used in the C3 step include potassium tert-butoxide, sodium tert-butoxide, sodium hydroxide, potassium hydroxide, etc.

[0087] And, since the number of reaction steps is small, a more specific and preferable production method is shown in the following reaction scheme.

[0088]

Chemical formula

[0089]

Chemical formula

[0090]

Chemical formula

[0091]

Chemical formula

[0092]

Chemical formula

[0093] [ka]

[0094] (where R 5 is represented by formula (1-I) 5 and n, R 13 is represented by n and R in formula (2). 13 It has the same meaning as The compound of the present invention can be dissolved in a solvent to form 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). In order to make the drying speed of the solvent suitable when forming an organic semiconductor layer, an organic solvent having a boiling point of 100° C. or higher at normal pressure is preferred.

[0095] The solvent that can be used in the present invention is not particularly limited. For example, aromatic hydrocarbons such as toluene, mesitylene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetralin, indane; aromatic ethers such as anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethyl phenyl ether, butyl phenyl ether, 1,2-methylenedioxybenzene, 1,2-ethylenedioxybenzene; aromatic halogen compounds such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene; heteroaromatics such as thiophene, 3-chlorothiophene, 2-chlorothiophene, 3-methylthiophene, 2-methylthiophene, benzothiophene, 2-methylbenzothiophene, 2,3-dihydrobenzothiophene, furan, 3-methylfuran, 2-methylfuran, 2,5-dimethylfuran, benzofuran, 2-methylbenzofuran, 2,3-dihydrobenzofuran, thiazole, oxazole, benzothiazole, benzoxazole, pyridine; saturated hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, 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, diethylene glycol monobutyl ether acetate;Esters such as dimethyl phthalate, diethyl phthalate, dimethyl terephthalate, phenyl acetate, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, γ-butyrolactone, etc.; cyclic ethers such as THF, 2-methoxymethyltetrahydrofuran, etc. can be mentioned. Among them, since it has an appropriate drying rate, preferably toluene, o-xylene, mesitylene, 1,2,4-trimethylbenzene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethyl phenyl ether, butyl phenyl ether, 1,2-methylenedioxybenzene, 1,2-ethylenedioxybenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 3-methylthiophene, benzothiazole, and more preferably, toluene, o-xylene, mesitylene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole.;

[0096] In addition, the solvent used in the present invention can be used alone as one kind of solvent, or two or more kinds of solvents having different properties such as boiling point, polarity, solubility parameter, etc. can be mixed and used.

[0097] When mixing and dissolving the aromatic compound represented by the formula (1-I) or the formula (1-II) in a solvent, for the purpose of promoting dissolution, it is preferably carried out in a temperature range of 0 to 80°C, and more preferably in a temperature range of 10 to 60°C.

[0098] Also, the time for dissolving and mixing the aromatic compound represented by the formula (1-I) or the formula (1-II) in an organic solvent is preferably 1 minute to 1 hour for obtaining a uniform solution.

[0099] In the present invention, when the concentration of the aromatic compound represented by the formula (1-I) or the formula (1-II) in the solution for forming the organic semiconductor layer of the present invention is in the range of 0.1 to 10.0% by weight, it becomes easy to handle and is excellent in efficiency when forming the organic semiconductor layer. Further, when the viscosity of the solution for forming the organic semiconductor layer is in the range of 0.3 to 10 mPa·s, more suitable coatability is exhibited.

[0100] Since the solution can be prepared at a relatively low temperature because the aromatic compound itself has appropriate aggregability and has oxidation resistance, it can be suitably applied to the production of organic thin films by a coating method. That is, since it is not necessary to remove air from the atmosphere, the coating process can be simplified. Further, the solution can contain, 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, polytriarylamine, poly(9,9-dioctylfluorene-co-dimethyltriarylamine), poly(N-vinylcarbazole), polymethyl methacrylate, poly(styrene-co-methyl methacrylate), polyethyl methacrylate, poly(n-propyl methacrylate), poly(isopropyl methacrylate), poly(n-butyl methacrylate), polyphenyl methacrylate, poly(methyl acrylate), poly(ethyl acrylate), poly(n-propyl acrylate), etc. Preferably, polymers such as polystyrene, poly(α-methylstyrene), poly(ethylene-co-norbornene), polymethyl methacrylate, polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, and methyl methacrylate-styrene copolymers can also be present as binders. The concentration of these polymer binders is preferably 0.001 to 10.0% by weight for an appropriate solution viscosity.

[0101] Since the glass transition temperature (Tg) of the polymer is suitable for the process temperature during the production of electronic devices, it is preferably 105°C or higher, more preferably 120°C or higher, and particularly preferably 150°C or higher.

[0102] In addition, the molecular weight of the polymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 20,000 to 100,000 because it is suitable for obtaining an organic thin film transistor with a higher carrier mobility. In the present invention, the molecular weight of the polymer refers to the weight average molecular weight (Mw) in terms of polystyrene.

[0103] The polymer has an effect as a general polymer binder and improves the film-forming property of the resulting organic semiconductor layer, and an insulating polymer and a semiconductor polymer can also be used.

[0104] More specifically, the polar cyclic polyolefins are more preferably polymers represented by the following formula (9).

[0105] [Chemical formula]

[0106] (Here, R 62 ~R 64 each independently represents one kind of a 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 kind of a 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. The bond consisting of a solid line and a dotted line represents a single bond or a double bond.) R 62 ~R 64Each independently represents one kind of group selected from 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. Due to the high heat resistance of the compound of the present invention, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms is preferred.

[0107] R 62 ~R 64 The alkyl group having 1 to 20 carbon atoms in R 60 ~R 63 and R 64 includes, for example, linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, etc. The aryl group having 6 to 20 carbon atoms includes, for example, phenyl group, p-tolyl group, p-(n-hexyl)phenyl group, p-(n-octyl)phenyl group, p-(2-ethylhexyl)phenyl group, etc. The alkyloxycarbonyl group having 2 to 20 carbon atoms includes, for example, methyloxycarbonyl group, ethyloxycarbonyl group, n-propyloxycarbonyl group, etc. The aryloxycarbonyl group having 7 to 20 carbon atoms includes, for example, phenoxycarbonyl group, 4-methylphenoxycarbonyl group, etc. The alkoxy group having 1 to 20 carbon atoms includes, for example, methoxy group, ethoxy group, n-propoxy group, etc. The aryloxy group having 6 to 20 carbon atoms includes, for example, phenoxy group, 4-methylphenoxy, etc. The alkylamino group having 1 to 20 carbon atoms includes, for example, methylamino group, ethylamino group, n-propylamino group, etc. Among them, due to the high heat resistance of the compound of the present invention, the substituent R

[0108] 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.

[0109] Examples of the halogen atom in the substituent Z include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, etc. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 2,4-dimethylphenoxycarbonyl group, a 4-ethylphenoxycarbonyl group, etc. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, etc. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a 4-methylphenoxy, etc. Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group, etc. Due to the high solubility and high heat resistance of the compound of the present invention, it is preferably an alkyloxycarbonyl group having 2 to 20 carbon atoms.

[0110] p represents an integer from 20 to 5,000, and is preferably from 40 to 2,000 because it is suitable for obtaining an organic thin film transistor with a larger carrier mobility. q represents an integer from 0 to 2, and is preferably 1. r represents an integer from 0 to 2, and is preferably 0 or 1. More preferably, it is 0.

[0111] The 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.

[0112] The polysulfones are not particularly limited as long as they have a polysulfone structure. More specifically, examples of the polysulfones include those represented by the following Polysulfones 1 to 5.

[0113]

Chemical formula

[0114] (Here, the substituents R 65 ~R 68 each independently represent an alkyl group having 1 to 20 carbon atoms, and s represents an integer of 10 to 20,000.) The alkyl group having 1 to 20 carbon atoms in the substituents R 65 ~R 68 includes, for example, linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl group, 2-hexyldecyl group, etc.

[0115] s represents an integer of 10 to 20,000, preferably an integer of 10 to 10,000.

[0116] The acrylonitrile-styrene copolymer is a copolymer of acrylonitrile and styrene in any ratio, exhibits good electrical properties, and has improved reliability such as a smaller change in the threshold voltage when subjected to bias stress. Therefore, the weight ratio of acrylonitrile to styrene is preferably in the range of 10:90 to 50:50, more preferably in the range of 20:80 to 40:60.

[0117] The methyl methacrylate-styrene copolymer is a copolymer of methyl methacrylate and styrene in any ratio, exhibits good electrical properties, and has improved reliability such as a smaller change in threshold voltage when subjected to bias stress. Therefore, the molar ratio of methyl methacrylate to styrene is preferably from 1:99 to 90:10, more preferably from 1:99 to 70:30.

[0118] As the polymer used as the polymer binder in the present invention, a polymer whose surface energy is adjusted with a surface treatment agent can be used. As the surface treatment agent, a silane coupling agent can be used. Specific examples thereof include, for example, 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, octyltrichlorosilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane and the like. The polymer used in the present invention can be used alone as one kind of polymer or as a mixture of two or more kinds of polymers. Furthermore, it is also possible to mix and use polymers having different molecular weights.

[0119] In the present invention, an organic semiconductor layer containing the compound of the present invention can be used. The organic semiconductor layer can be formed by applying the solution for forming the organic semiconductor layer.

[0120] As the coating method when forming the organic semiconductor layer using the solution for forming the organic semiconductor layer containing the compound of the present invention, there is no particular limitation as long as it is a method capable of forming the organic semiconductor layer. For example, simple coating methods such as spin coating, drop casting, dip coating, and cast coating; printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing can be mentioned. Among them, spin coating, drop casting, and inkjet are preferred because an organic semiconductor layer can be easily and efficiently formed.

[0121] After applying the solution for forming an organic semiconductor layer of the present invention and drying and removing the solvent, it is possible to form an organic semiconductor layer containing the compound of the present invention using the solution for forming an organic semiconductor layer.

[0122] When drying and removing the solvent from the applied organic semiconductor layer, there are no particular restrictions on the drying conditions. For example, it is possible to dry and remove the solvent under normal pressure or reduced pressure.

[0123] There are no particular restrictions on the temperature for drying and removing the organic solvent from the applied organic semiconductor layer. However, since the organic solvent can be efficiently dried and removed from the applied organic semiconductor layer and an organic semiconductor layer can be formed, it is preferably carried out in the temperature range of 10 to 150°C.

[0124] When drying and removing the organic solvent from the applied organic semiconductor layer, it is possible to control the crystal growth of the aromatic compound represented by formula (1-I) or formula (1-II) by adjusting the vaporization rate of the organic solvent to be removed.

[0125] There is no restriction on the film thickness of the organic semiconductor layer formed by the solution for forming an organic semiconductor layer of the present invention. Since good carrier mobility can be obtained, it is preferably in the range of 1 nm to 1 μm, and more preferably in the range of 10 nm to 300 nm.

[0126] In addition, the obtained organic semiconductor layer may be annealed at 40 to 180°C after forming the organic semiconductor layer.

[0127] The organic semiconductor layer formed from the solution for forming an organic semiconductor layer of the present invention can be used as an organic semiconductor device including the organic semiconductor layer, particularly an organic thin-film transistor containing the compound of the present invention including the organic semiconductor layer.

[0128] An organic thin film transistor can be obtained by laminating, via an insulating layer, an organic semiconductor layer with source and drain electrodes provided thereon and a gate electrode on a substrate. By using, for the organic semiconductor layer, an organic semiconductor layer formed with the solution for forming an organic semiconductor layer of the present invention, it is possible to obtain an organic thin film transistor that exhibits excellent semiconductor and electrical characteristics.

[0129] Fig. 1 shows the structure according to the cross-sectional shape of a general organic thin film transistor. 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, where 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. The organic semiconductor layer formed from the solution for forming an organic semiconductor layer of the present invention can be applied to any of these organic thin film transistors.

[0130] The substrate according to the present invention is not particularly limited. For example, plastic substrates such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, fluorinated cyclic polyolefin, polyimide, polycarbonate, polyvinyl phenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyether sulfone, polyphenylene sulfide, and cellulose triacetate; inorganic material substrates such as glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum pentoxide, indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum can be mentioned. When highly doped silicon is used as the substrate, the substrate can also serve as the gate electrode.

[0131] The gate electrode according to the present invention is not particularly limited. For example, 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 (for example, PEDOT-PSS) can be mentioned.

[0132] In addition, the above inorganic materials can also be used as metal nanoparticle inks. In this case, the solvent is a polar solvent such as water, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, etc. for appropriate dispersibility; an aliphatic hydrocarbon solvent having 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, tetradecane, etc.; 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, 3,4-dimethylanisole, etc. It is preferably this. After applying the nanoparticle ink, it is preferably annealed in the temperature range of 80°C to 200°C to improve conductivity.

[0133] The gate insulating layer according to the present invention is not particularly limited. For example, 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, bismuth titanate; polymethyl methacrylate, polymethyl acrylate, polyimide, polyamic acid polycarbonate, polyvinyl phenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), polyethylene terephthalate, polyethylene naphthalate, ethyl polycinnamate, methyl polycinnamate, ethyl polycrotonate, 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 (registered trademark), Teflon (registered trademark), and parylene (registered trademark) such as parylene C can be mentioned. Since the manufacturing method is simple, it is preferably a polymer insulating material (polymer gate insulating layer) to which the coating method can be applied.

[0134] The solvent used to dissolve the polymer insulating material is not particularly limited. For example, 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; glycol solvents 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, 1,6-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; fluorinated solvents such as perfluorohexane, perfluorooctane, 2-(pentafluoroethyl)hexane, and 3-(pentafluoroethyl)heptane, etc. can be mentioned.

[0135] 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 limitation on the film thickness of the insulating layer obtained at this concentration. From the viewpoint of insulation resistance, it is preferably 100 nm to 1 μm, more preferably 150 nm to 900 nm.

[0136] And the surfaces of these gate insulating layers can also be used after being modified with silanes such as octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, octylphosphonic acid; silylamines such as hexamethyldisilazane. Generally, by performing surface treatment on the gate insulating layer, favorable results such as an increase in the crystal grain size of the organic semiconductor material, improvement in molecular orientation, improvement in carrier mobility, improvement in current on / off ratio, and reduction in threshold voltage can be obtained.

[0137] There is no particular limitation on the materials for the source electrode and drain electrode of the organic thin film transistor of the present invention, and the same materials as those for the gate electrode can be used, which may be the same as or different from the materials for the gate electrode, and different materials may be laminated. Also, in order to increase the injection efficiency of carriers, surface treatment can be performed on these electrode materials. Examples of the surface treatment agent used for surface treatment include benzenethiol, pentafluorobenzenethiol, 4-fluorobenzenethiol, 4-methoxybenzenethiol, and the like.

[0138] Due to the fast operability, the organic thin film transistor of the present invention preferably has a carrier mobility of 0.10 cm 2 / V·sec or more, and preferably has a threshold voltage in the range of -3V to +3V due to low power consumption.

[0139] The organic thin film transistor of the present invention can be used in applications of organic semiconductor layers of transistors such as electronic paper, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, biosensors, etc.; organic EL display materials; organic semiconductor laser materials; organic thin film solar cell materials; photonic crystal materials; semiconductor materials for imaging devices, etc. Since the aromatic compound represented by the formula (1-I) or the formula (1-II) forms a crystalline thin film, it is preferably used as a semiconductor layer application of an organic thin film transistor.

Examples

[0140] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0141] For the identification of the product 1 1H NMR spectrum and liquid chromatography-mass spectrometry (LCMS) analysis were used.

[0142] < 1 1H NMR spectrum analysis> Apparatus; manufactured by JEOL, (trade name) Delta V5 (400 MHz) Measurement temperature; 23 °C (when no temperature is specified) <Liquid chromatography-mass spectrometry (LCMS) analysis> Apparatus; Bruker Daltonics, (trade name) microTOF focus MS ionization; atmospheric pressure chemical ionization (APCI) method LC conditions; the conditions described in the items of the following liquid chromatography analysis For the confirmation of the progress of the reaction, etc., thin layer chromatography, gas chromatography (GC), and liquid chromatography (LC) analysis were used. Liquid chromatography analysis was also used for the purity measurement of the aromatic compound.

[0143] <Thin layer chromatography analysis> Merck's PLC silica gel 60F254 0.5mm for thin-layer chromatography was used, and hexane or / and toluene was used as the developing solvent.

[0144] <Gas chromatography analysis> Apparatus; manufactured by Shimadzu Corporation, (trade name) GC2025 Column; manufactured by RESTEK Corporation, (trade name) Rxi-1HT, 30m <Liquid chromatography analysis> Apparatus; manufactured by Agilent Technologies, model; 1260 Infinity II Column; manufactured by Tosoh Corporation, (trade name) ODS-100V, 5μm, 4.6mm×250mm Column temperature; 33°C Eluent; dichloromethane:acetonitrile = 2:8 (volume ratio) Flow rate; 1.0 ml / min A recycling preparative HPLC apparatus was used for the purification of aromatic compounds.

[0145] <Recycling preparative HPLC> Apparatus; manufactured by Japan Analytical Industry Co., Ltd., model; LC-9160II NEXT Solvent; tetrahydrofuran Flow rate; 10 ml / min A differential scanning calorimeter (DSC) was used for measuring the melting point of aromatic compounds.

[0146] <DSC measurement> Apparatus; manufactured by SII NanoTechnology Inc., model; DSC6220 Heating and cooling rate; 10°C / min Scanning range; -10°C to 300°C A semiconductor parameter analyzer was used for evaluating the transport properties of aromatic compounds.

[0147] <Transport property measurement> Apparatus; manufactured by Keysight Technologies, model; 4200A-SCS Drain voltage; -20V Gate voltage; 10V to -20V Synthesis Example 1 2-Bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene Under a nitrogen atmosphere, 148 mg (0.328 mmol) of 2-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 17 in the said publication) synthesized by the method described in WO2021 / 177417 and 8.0 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, 0.75 mL (1.20 mmol) of 1.6 M n-butyllithium (FUJIFILM Wako Pure Chemical Industries) was added, and the mixture was stirred at -78 °C for 15 minutes and at room temperature for 3 hours. 428 mg (1.32 mmol) of 1,2-dibromotetrachloroethane was added at -78 °C and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, the solid was filtered, washed with water and methanol, and 174 mg of a yellow solid of 2-bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene was obtained (yield 84%). 2-Bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene

[0148] [Chemical formula]

[0149] Synthesis of Example 1 2-(4-n-butylphenethyl)-8-propylanthra[1,2-b:5,6-b']dithiophene (Compound 1) Under a nitrogen atmosphere, 40.7 mg (0.064 mmol) of 2-bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 1, 6.8 mg (0.030 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Corporation), 27.6 mg (0.0591 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), 34.6 mg (0.308 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.) and 23.4 mg (0.266 mmol) of propylboronic acid (Tokyo Chemical Industry Co., Ltd.) were added to a 50 mL Schlenk tube. 5.0 mL of toluene (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) and 0.5 mL of water were added thereto, and the mixture was stirred at 80 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, insolubles were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Corporation), and the resulting solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: he xane). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 4.1 mg of a yellow solid of 2-(4-n-butylphenethyl)-8-propylanthra[1,2-b:5,6-b']dithiophene (Compound 1) (yield 13%).

[0150] 1 H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.8 Hz, 2H), 7.71 (d, J = 7.9 Hz, 1H), 7.69 (d, J = 8.7 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.31 (t, J = 7.6 Hz, 2H), 3.11 (t, J = 8.6 Hz, 2H), 3.00 (t, J = 7.2 Hz, 2H), 2.60 (t, J = 7.8 Hz, 2H), 1.89 - 1.84 (m, 2H), 1.65 - 1.57 (m, 2H), 1.41 - 1.32 (m, 2H), 1.08 (t, J = 7.3 Hz, 3H), 0.94 (t, J = 7.3 Hz, 3H).

[0151] Melting point: 159 °C (Compound 1)

[0152]

Chemical Structure

[0153] Example 2 Synthesis of 2-Butyl-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 2) Under a nitrogen atmosphere, 40.2 mg (0.0634 mmol) of 2-bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 1, 5.9 mg (0.026 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Corporation), 23.3 mg (0.0499 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), 24.8 mg (0.221 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.), and 21.4 mg (0.210 mmol) of butylboronic acid (Tokyo Chemical Industry Co., Ltd.) were added to a 50 mL Schlenk tube. 5.0 mL of toluene (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) and 0.5 mL of water were added thereto, and the mixture was stirred at 80 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Corporation), and the obtained solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 3.4 mg of a yellow solid of 2-butyl-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 2) (yield 10%).

[0154] 1 H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 9.0 Hz, 2H), 7.70 (d, J = 8.8 Hz, 1H), 7.69 (d, J = 8.9 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.32 (t, J = 7.4 Hz, 2H), 3.11 (t, J = 8.5 Hz, 2H), 3.02 (t, J = 7.6 Hz, 2H), 2.60 (t, J = 7.7 Hz, 2H), 1.86 - 1.79 (m, 2H), 1.65 - 1.57 (m, 2H), 1.52 - 1.45 (m, 2H), 1.42 - 1.32 (m, 2H), 1.00 (t, J = 7.4 Hz, 3H), 0.94 (t, J = 7.4 Hz, 3H). (Compound 2)

[0155] [Chemical]

[0156] Example 3 Synthesis of 2-(4-n-butylphenethyl)-8-pentylanthra[1,2-b:5,6-b']dithiophene (Compound 3) Under a nitrogen atmosphere, 41.5 mg (0.065 mmol) of 2-bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 1, 5.2 mg (0.023 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Industries, Ltd.), 18.5 mg (0.0396 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), 29.4 mg (0.262 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.) and 25.9 mg (0.223 mmol) of pentylboronic acid (Tokyo Chemical Industry Co., Ltd.) were added to a 50 mL Schlenk tube. 5.0 mL of toluene (FUJIFILM Wako Pure Chemical Industries, Ltd., dehydrated grade) and 1.0 mL of water were added thereto, and the mixture was stirred at 80 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Industries, Ltd.), and the obtained solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 4.9 mg of a yellow solid of 2-(4-n-butylphenethyl)-8-pentylanthra[1,2-b:5,6-b']dithiophene (Compound 3) (yield 14%).

[0157] 1 1H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.7 Hz, 1H), 7.84 (d, J = 8.7 Hz, 1H), 7.71 (d, J = 8.8 Hz, 1H), 7.69 (d, J = 8.7 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.32 (t, J = 7.7 Hz, 2H), 3.12 (t, J = 8.5 Hz, 2H), 3.01 (t, J = 7.2 Hz, 2H), 2.60 (t, J = 7.7 Hz, 2H), 1.87 - 1.80 (m, 2H), 1.65 - 1.57 (m, 2H), 1.49 - 1.32 (m, 6H), 0.96 - 0.92 (m, 6H). (Compound 3)

[0158]

Chem.

[0159] Example 4 Synthesis of 2-(4-n-butylphenethyl)-8-hexylanthra[1,2-b:5,6-b']dithiophene (Compound 4) Under a nitrogen atmosphere, 44.8 mg (0.0706 mmol) of 2-bromo-8-(4-n-butylphenethyl)anthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 1, 5.3 mg (0.024 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Corporation), 20.0 mg (0.0429 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), 31.5 mg (0.281 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.), and 31.2 mg (0.240 mmol) of hexylboronic acid (Tokyo Chemical Industry Co., Ltd.) were added to a 50 mL Schlenk tube. 5.0 mL of toluene (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) and 0.5 mL of water were added thereto, and the mixture was stirred at 80 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Corporation), and the obtained solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 5.9 mg of a yellow solid of 2-(4-n-butylphenethyl)-8-hexylanthra[1,2-b:5,6-b']dithiophene (Compound 4) (yield 15%).

[0160] 11H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.6 Hz, 1H), 7.84 (d, J = 8.7 Hz, 1H), 7.70 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.32 (t, J = 7.6 Hz, 2H), 3.11 (t, J = 8.6 Hz, 2H), 3.01 (t, J = 7.7 Hz, 2H), 2.60 (t, J = 7.7 Hz, 2H), 1.87 - 1.80 (m, 2H), 1.65 - 1.57 (m, 2H), 1.48 - 1.43 (m, 2H), 1.40 - 1.32 (m, 6H), 0.96 - 0.90 (m, 6H).

[0161] Melting point: 154 °C (Compound 4)

[0162]

Chem.

[0163] Synthesis Example 2 Synthesis of 2-Hexylanthra[1,2-b:5,6-b']dithiophene Under a nitrogen atmosphere, 716 mg (purity 65%, 1.26 mmol) of 2-Bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22 in the said publication) synthesized by the method described in WO2021 / 177417, 67.0 mg (0.298 mmol) of Palladium(II) Acetate (FUJIFILM Wako Pure Chemical Corporation), 278 mg (0.596 mmol) of Ruphos (Tokyo Chemical Industry), 487 mg (3.64 mmol) of Potassium tert-Butoxide (Tokyo Chemical Industry), and 509 mg (3.91 mmol) of Hexylboronic Acid (Tokyo Chemical Industry) were added to a 200 mL Schlenk tube. 45 mL of Toluene (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) and 3.0 mL of water were added thereto, and the mixture was stirred at 80 °C for 2.5 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using Celite (FUJIFILM Wako Pure Chemical Corporation), and the obtained solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane) to obtain 100 mg of a yellow solid of 2-Hexylanthra[1,2-b:5,6-b']dithiophene (yield 49%).

[0164] 1 1H NMR (CDCl3): δ = 8.70 (s, 1H), 8.62 (s, 1H), 7.89 (d, J = 6.6 Hz, 1H), 7.87 (d, J = 6.4 Hz, 1H), 7.82 (d, J = 8.7 Hz, 1H), 7.73 (d, J = 8.7 Hz, 1H), 7.54 (d, J = 5.2 Hz, 1H), 7.49 (d, J = 5.1 Hz, 1H), 7.16 (s, 1H), 3.02 (t, J = 8.0 Hz, 2H), 1.91 (dt, J = 7.6 Hz, J = 7.6 Hz, 2H), 1.51 - 1.44 (m, 2H), 1.39 - 1.32 (m, 4H), 0.94 - 0.90 (m, 3H). (2-Hexylanthra[1,2-b:5,6-b']dithiophene)

[0165]

Chem.

[0166] Synthesis Example 3 2-Bromo-8-hexylanthra[1,2-b:5,6-b']dithiophene Under a nitrogen atmosphere, 246 mg (0.655 mmol) of 2-hexylanthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 2 and 10 ml of THF (FUJIFILM Wako Pure Chemical Industries, dehydration grade) were added to a 50 ml Schlenk reaction vessel. The mixture was cooled to -78 °C, 1.50 mL (2.40 mmol) of 1.6 M n-butyllithium (FUJIFILM Wako Pure Chemical Industries) was added, and the mixture was stirred at -78 °C for 3 hours. 864 mg (2.65 mmol) of 1,2-dibromotetrachloroethane was added at -78 °C, and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, the solid was filtered, washed with water and methanol, and 234 mg of a yellow solid of 2-bromo-8-hexylanthra[1,2-b:5,6-b']dithiophene was obtained (yield 78%).

[0167] 11H NMR (CDCl3): δ = 8.59 (s, 1H), 8.52 (s, 1H), 7.87 (d, J = 6.0 Hz, 1H), 7.84 (d, J = 6.0 Hz, 1H), 7.73 (d, J = 8.9 Hz, 1H), 7.68 (d, J = 8.8 Hz, 1H), 7.46 (s, 1H), 7.16 (s, 1H), 3.01 (t, J = 7.3 Hz, 2H), 1.83 (dt, J = 7.6 Hz, J = 7.6 Hz, 2H), 1.49 - 1.43 (m, 2H), 1.39 - 1.32 (m, 4H), 0.94 - 0.90 (m, 3H). (2-Bromo-8-hexylanthra[1,2-b:5,6-b’]dithiophene)

[0168] [Chemical formula]

[0169] Synthesis Example 4 Synthesis of 2-(4-propylphenethyl)ethan-1-ol Under a nitrogen atmosphere, 4.27 g (21.5 mmol) of 1-bromo-4-propylbenzene (Tokyo Chemical Industry) and 80 mL of THF (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 300 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, 22.0 mL (35.2 mmol) of 1.6 M n-butyllithium (Fuji Film Wako Pure Chemical Industries) was added, and the mixture was stirred at -78 °C for 3.5 hours. To this solution, 25.0 mL (30.0 mmol) of a 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78 °C, and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added at 0 °C, and toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; dichloromethane) to obtain 2.31 g of a colorless liquid of 2-(4-propylphenethyl)ethan-1-ol (yield 63%).

[0170] 11H NMR (CDCl3): δ = 7.16 (s, 4H), 3.85 (t, J = 6.5 Hz, 2H), 2.85 (t, J = 6.6 Hz, 2H), 2.58 (t, J = 7.6 Hz, 2H), 1.69 - 1.60 (m, 2H), 1.54 (brs, 1H), 0.96 (t, J = 7.3 Hz, 3H). (2-(4-Propylphenethyl)ethan-1-ol)

[0171]

Chemical formula

[0172] Synthesis Example 5 Synthesis of 1-(2-Bromoethyl)-4-propylbenzene Under a nitrogen atmosphere, 2.31 g (14.1 mmol) of 2-(4-propylphenethyl)ethan-1-ol synthesized in Synthesis Example 4 and 20 ml of toluene (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 100 ml three-necked flask. To this solution, 0.700 ml (7.37 mmol) of phosphorus tribromide (Fuji Film Wako Pure Chemical Industries) was added at room temperature, and the mixture was stirred for 10 minutes and then stirred at 100 °C for 3 hours. The reaction solution was poured into ice, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and then toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and 2.61 g of a colorless liquid of 1-(2-bromoethyl)-4-propylbenzene was obtained (yield 81%).

[0173] 1 1H NMR (CDCl3): δ = 7.14 (s, 4H), 3.56 (t, J = 7.6 Hz, 2H), 3.14 (t, J = 7.8 Hz, 2H), 2.58 (t, J = 7.5 Hz, 2H), 1.69 - 1.56 (m, 2H), 0.96 (t, J = 7.3 Hz, 3H). (1-(2-Bromoethyl)-4-propylbenzene)

[0174]

Chemical formula

[0175] Synthesis Example 6 Synthesis of 4,4,5,5-Tetramethyl-2-(4-propylphenethyl)-1,3,2-dioxaborolane Under a nitrogen atmosphere, 303 mg (0.524 mmol) of Xantphos (Tokyo Chemical Industry), 3.16 g (12.5 mmol) of bis(pinacolato)diboron (Tokyo Chemical Industry), 52.1 mg (0.526 mmol) of copper(I) chloride (Fuji Film Wako Pure Chemical Industries), 1.39 g (12.4 mmol) of potassium tert-butoxide (Tokyo Chemical Industry) and 6 ml of THF (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 50 ml Schlenk reaction vessel and stirred at room temperature for 20 minutes. Under ice-cooling, 4.0 mL of a THF solution (Fuji Film Wako Pure Chemical Industries, dehydrated grade) of 2.35 g (10.3 mmol) of 1-(2-bromoethyl)-4-propylbenzene synthesized in Synthesis Example 5 was added, and the mixture was stirred at 0 °C for 20 minutes and at room temperature for 3 hours. The reaction mixture was ice-cooled, water was added, and then toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene) to obtain 2.44 g of a yellow liquid of 4,4,5,5-tetramethyl-2-(4-propylphenethyl)-1,3,2-dioxaborolane (yield 85%).

[0176] 1 H NMR (CDCl3): δ = 7.12 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H), 2.72 (t, J = 8.0 Hz, 2H), 2.54 (t, J = 7.4 Hz, 2H), 1.67 - 1.56 (m, 2H), 1.22 (s, 12H), 1.13 (t, J = 8.3 Hz, 2H), 0.93 (t, J = 7.3 Hz, 3H). (4,4,5,5-Tetramethyl-2-(4-propylphenethyl)-1,3,2-dioxaborolane)

[0177]

Chemical Structure

[0178] Example 5 Synthesis of 2-Hexyl-8-(4-propylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 5) Under a nitrogen atmosphere, 37.9 mg (0.0836 mmol) of 2-bromo-8-hexylanthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 3, 5.8 mg (0.026 mmol) of palladium(II) acetate (Fuji Film Wako Pure Chemical Industries), 23.5 mg (0.0504 mmol) of Ruphos (Tokyo Chemical Industry), and 33.0 mg (0.294 mmol) of potassium tert-butoxide (Tokyo Chemical Industry) were added to a 50 mL Schlenk tube. To this, a solution of 77.2 mg (0.282 mmol) of 4,4,5,5-tetramethyl-2-(4-propylphenethyl)-1,3,2-dioxaborolane synthesized in Synthesis Example 6 in 5.0 mL of toluene (Fuji Film Wako Pure Chemical Industries, dehydrated grade) and 0.5 mL of water were added, and the mixture was stirred at 80 °C for 18 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (Fuji Film Wako Pure Chemical Industries), and the resulting solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was recrystallized and purified from heptane to obtain 11.2 mg (yield 26%) of a yellow solid of 2-hexyl-8-(4-propylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 5).

[0179] 1 H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.8 Hz, 2H), 7.71 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.7 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.32 (t, J = 6.8 Hz, 2H), 3.12 (t, J = 6.4 Hz, 2H), 3.01 (t, J = 7.8 Hz, 2H), 2.58 (t, J = 7.4 Hz, 2H), 1.87 - 1.80 (m, 2H), 1.70 - 1.60 (m, 2H), 1.51 - 1.43 (m, 2H), 1.38 - 1.35 (m, 4H), 0.98 - 0.90 (m, 6H).

[0180] Melting point: 164 °C (Compound 5)

[0181]

Chemical Structure

[0182] Synthesis Example 7 Synthesis of 2-(4-Pentylphenethyl)ethan-1-ol Under a nitrogen atmosphere, 5.02 g (22.1 mmol) of 1-bromo-4-pentylbenzene (Tokyo Chemical Industry) and 80 mL of THF (Fuji Film Wako Pure Chemical Industries, dehydration grade) were added to a 300 mL Schlenk reaction vessel. The mixture was cooled to -78 °C, 20.0 mL (32.0 mmol) of 1.6 M n-butyllithium (Fuji Film Wako Pure Chemical Industries) was added, and the mixture was stirred at -78 °C for 1.5 hours. To this solution, 25.0 mL (30.0 mmol) of a 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78 °C, and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added thereto at 0 °C, and toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; dichloromethane, ethyl acetate) to obtain 1.84 g of a colorless liquid of 2-(4-pentylphenethyl)ethan-1-ol (yield 42%).

[0183] 1 H NMR (CDCl3): δ = 7.12 (s, 4H), 3.83 (t, J = 6.6 Hz, 2H), 2.83 (t, J = 6.5 Hz, 2H), 2.57 (t, J = 7.6 Hz, 2H), 1.64 - 1.56 (m, 2H), 1.50 (brs, 1H), 1.36 - 1.30 (m, 4H), 0.89 (t, J = 6.9 Hz, 3H). (2-(4-Pentylphenethyl)ethan-1-ol)

[0184] [Chemical Structure Diagram]

[0185] Synthesis Example 8 Synthesis of 1-(2-Bromoethyl)-4-pentylbenzene Under a nitrogen atmosphere, 2.27 g (11.8 mmol) of 2-(4-pentylphenethyl)ethan-1-ol synthesized in Synthesis Example 7 and 20 ml of toluene (Fuji Film Wako Pure Chemical Industries, dehydration grade) were added to a 100 ml three-necked flask. To this solution, 0.560 ml (5.90 mmol) of phosphorus tribromide (Fuji Film Wako Pure Chemical Industries) was added at room temperature, and after stirring for 10 minutes, the mixture was stirred at 100 °C for 3 hours. The reaction solution was poured into ice, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and then toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; dichloromethane) to obtain 2.51 g of a colorless liquid of 1-(2-bromoethyl)-4-pentylbenzene (yield 81%).

[0186] 1 1H NMR (CDCl3): δ = 7.15 - 7.11 (m, 4H), 3.56 (t, J = 7.4 Hz, 2H), 3.14 (t, J = 7.9 Hz, 2H), 2.59 (t, J = 7.7 Hz, 2H), 1.65 - 1.56 (m, 2H), 1.37 - 1.31 (m, 4H), 0.90 (t, J = 6.8 Hz, 3H). (1-(2-Bromoethyl)-4-pentylbenzene)

[0187]

Chemical Structure

[0188] Synthesis Example 9 Synthesis of 4,4,5,5-tetramethyl-2-(4-pentylphenethyl)-1,3,2-dioxaborolane Under a nitrogen atmosphere, 124 mg (0.214 mmol) of Xantphos (Tokyo Chemical Industry), 1.22 g (4.79 mmol) of bis(pinacolato)diboron (Tokyo Chemical Industry), 21.0 mg (0.21 mmol) of copper(I) chloride (Fuji Film Wako Pure Chemical Industries), 533 mg (4.75 mmol) of potassium tert-butoxide (Tokyo Chemical Industry) and 8 ml of THF (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 50 ml Schlenk reaction vessel and stirred at room temperature for 25 minutes. Under ice-cooling, 2.0 mL of a THF solution (Fuji Film Wako Pure Chemical Industries, dehydrated grade) of 1.00 g (3.92 mmol) of 1-(2-bromoethyl)-4-pentylbenzene synthesized in Synthesis Example 8 was added, and the mixture was stirred at 0 °C for 25 minutes and at room temperature for 3 hours. The reaction mixture was ice-cooled, water was added, and then toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene) to obtain 908 mg of a colorless liquid of 4,4,5,5-tetramethyl-2-(4-pentylphenethyl)-1,3,2-dioxaborolane (yield 74%). 1H- 1 H NMR (CDCl3): δ = 7.12 (d, J = 8.2 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 2.71 (t, J = 8.2 Hz, 2H), 2.55 (t, J = 7.8 Hz, 2H), 1.63 - 1.55 (m, 2H), 1.37 - 1.28 (m, 4H), 1.22 (s, 12H), 1.13 (t, J = 8.2 Hz, 2H), 0.88 (t, J = 7.1 Hz, 3H). (4,4,5,5-Tetramethyl-2-(4-pentylphenethyl)-1,3,2-dioxaborolane)

[0189]

Chemical Structure

[0190] Example 6 Synthesis of 2-Hexyl-8-(4-pentylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 6) Under a nitrogen atmosphere, 41.4 mg (0.0913 mmol) of 2-bromo-8-hexylanthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 3, 4.3 mg (0.019 mmol) of palladium(II) acetate (Fuji Film Wako Pure Chemical Industries), 23.0 mg (0.0493 mmol) of Ruphos (Tokyo Chemical Industry), and 46.0 mg (0.410 mmol) of potassium tert-butoxide (Tokyo Chemical Industry) were added to a 50 mL Schlenk tube. To this, a solution of 108 mg (0.358 mmol) of 4,4,5,5-tetramethyl-2-(4-pentylphenethyl)-1,3,2-dioxaborolane synthesized in Synthesis Example 9 in 5.0 mL of toluene (Fuji Film Wako Pure Chemical Industries, dehydrated grade) and 0.5 mL of water were added, and the mixture was stirred at 80 °C for 22 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (Fuji Film Wako Pure Chemical Industries), and the resulting solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 24.9 mg (yield 49%) of a yellow solid of 2-hexyl-8-(4-pentylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 6).

[0191] 1 H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 9.6 Hz, 2H), 7.70 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.7 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.31 (t, J = 8.0 Hz, 2H), 3.11 (t, J = 7.8 Hz, 2H), 3.01 (t, J = 7.8 Hz, 2H), 2.59 (t, J = 7.8 Hz, 2H), 1.86 - 1.79 (m, 2H), 1.65 - 1.58 (m, 2H), 1.50 - 1.44 (m, 2H), 1.37 - 1.32 (m, 8H), 0.93 - 0.88 (m, 6H).

[0192] Melting point: 151 °C (Compound 6)

[0193]

Chemical Structure

[0194] Synthesis Example 10 Synthesis of 2-(4-hexylphenethyl)ethan-1-ol Under a nitrogen atmosphere, 4.93 g (20.4 mmol) of 1-bromo-4-hexylbenzene (Tokyo Chemical Industry) and 80 ml of THF (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 300 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 22.0 mL (35.2 mmol) of 1.6 M n-butyllithium (Fuji Film Wako Pure Chemical Industries) was added, and the mixture was stirred at -78°C for 3.0 hours. To this solution, 25.0 mL (30.0 mmol) of a 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78°C, and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added at 0°C, and toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; dichloromethane, ethyl acetate) to obtain 2.87 g of a colorless liquid of 2-(4-hexylphenethyl)ethan-1-ol (yield 66%).

[0195] 1 H NMR (CDCl3): δ = 7.13 (s, 4H), 3.87 - 3.83 (m, 2H), 2.84 (t, J = 6.4 Hz, 2H), 2.58 (t, J = 7.8 Hz, 2H), 1.63 - 1.56 (m, 2H), 1.37 - 1.24 (m, 7H), 0.88 (t, J = 6.9 Hz, 3H). (2-(4-hexylphenethyl)ethan-1-ol)

[0196]

Chemical Structure

[0197] Synthesis Example 11 Synthesis of 1-(2-bromoethyl)-4-hexylbenzene Under a nitrogen atmosphere, 2.87 g (13.9 mmol) of 2-(4-hexylphenethyl)ethan-1-ol synthesized in Synthesis Example 10 and 20 ml of toluene (Fuji Film Wako Pure Chemical Industries, dehydration grade) were added to a 100 ml three-necked flask. To this solution, 0.670 ml (7.05 mmol) of phosphorus tribromide (Fuji Film Wako Pure Chemical Industries) was added at room temperature, and the mixture was stirred for 30 minutes and then stirred at 100 °C for 3 hours and 20 minutes. The reaction solution was poured into ice, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and then toluene was added for phase separation. The organic phase was washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and 433 mg of a colorless liquid of 1-(2-bromoethyl)-4-hexylbenzene was obtained (yield 12%).

[0198] 1 1H NMR (CDCl3): δ = 7.16 - 7.09 (m, 4H), 3.55 (t, J = 7.8 Hz, 2H), 3.13 (t, J = 7.8 Hz, 2H), 2.58 (t, J = 7.8 Hz, 2H), 1.63 - 1.55 (m, 2H), 1.38 - 1.25 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H). (1-(2-Bromoethyl)-4-pentylbenzene)

[0199]

Chemical formula

[0200] Synthesis Example 12 Synthesis of 4,4,5,5-tetramethyl-2-(4-hexylphenethyl)-1,3,2-dioxaborolane Under a nitrogen atmosphere, 61.4 mg (0.106 mmol) of Xantphos (Tokyo Chemical Industry), 498 mg (1.96 mmol) of bis(pinacolato)diboron (Tokyo Chemical Industry), 10.4 mg (0.105 mmol) of copper(I) chloride (Fuji Film Wako Pure Chemical Industries), 200 mg (1.8 mmol) of potassium tert-butoxide (Tokyo Chemical Industry) and 3.3 ml of THF (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added to a 50 ml Schlenk reaction vessel and stirred at room temperature for 30 minutes. Under ice-cooling, 1.0 mL of a THF solution (Fuji Film Wako Pure Chemical Industries, dehydrated grade) of 403 mg (1.50 mmol) of 1-(2-bromoethyl)-4-pentylbenzene synthesized in Synthesis Example 11 was added, and the mixture was stirred at 0 °C for 10 minutes and at room temperature for 3 hours and 30 minutes. The reaction mixture was ice-cooled, water was added, and then 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 obtained residue was purified by silica gel column chromatography (solvent; toluene) to obtain 341 mg of a yellow liquid of 4,4,5,5-tetramethyl-2-(4-hexylphenethyl)-1,3,2-dioxaborolane (yield 69%).

[0201] 1 1H NMR (CDCl3): δ = 7.12 (d, J = 8.2 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 2.71 (t, J = 8.2 Hz, 2H), 2.55 (t, J = 7.8 Hz, 2H), 1.62 - 1.54 (m, 2H), 1.37 - 1.25 (m, 6H), 1.22 (s, 12H), 1.13 (t, J = 8.2 Hz, 2H), 0.88 (t, J = 6.9 Hz, 3H). (4,4,5,5-Tetramethyl-2-(4-hexylphenethyl)-1,3,2-dioxaborolane)

[0202]

Chemical Structure

[0203] Example 7 Synthesis of 2-Hexyl-8-(4-hexylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 7) Under a nitrogen atmosphere, 39.1 mg (0.0862 mmol) of 2-bromo-8-hexylanthra[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 3, 6.3 mg (0.028 mmol) of palladium(II) acetate (Fuji Film Wako Pure Chemical Industries), 26.8 mg (0.0574 mmol) of Ruphos (Tokyo Chemical Industry), and 358 mg (0.319 mmol) of potassium tert-butoxide (Tokyo Chemical Industry) were added to a 50 mL Schlenk tube. To this, a solution of 91.0 mg (0.288 mmol) of 4,4,5,5-tetramethyl-2-(4-hexylphenethyl)-1,3,2-dioxaborolane synthesized in Synthesis Example 12 in 5.0 mL of toluene (Fuji Film Wako Pure Chemical Industries, dehydrated grade) and 0.5 mL of water were added, and the mixture was stirred at 80 °C for 22 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (Fuji Film Wako Pure Chemical Industries), and the resulting solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 27.3 mg (yield 56%) of a yellow solid of 2-hexyl-8-(4-hexylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 7).

[0204] 1 H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.7 Hz, 1H), 7.84 (d, J = 8.7 Hz, 1H), 7.71 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.7 Hz, 1H), 7.19 - 7.12 (m, 6H), 3.31 (t, J = 8.0 Hz, 2H), 3.11 (t, J = 8.0 Hz, 2H), 3.01 (t, J = 7.5 Hz, 2H), 2.59 (t, J = 7.8 Hz, 2H), 1.86 - 1.79 (m, 2H), 1.65 - 1.57 (m, 2H), 1.48 - 1.44 (m, 2H), 1.38 - 1.30 (m, 10H), 0.93 - 0.87 (m, 6H).

[0205] Melting point: 151 °C (Compound 7)

[0206]

Chemical Structure

[0207] Synthesis Example 13 Synthesis of 4,4,5,5 - Tetramethyl - 2 - (4 - octylphenylethyl) - 1,3,2 - dioxaborolane Under a nitrogen atmosphere and ice cooling, 52.0 mL (46.8 mmol) of an 8.5% borane / THF solution (Tokyo Chemical Industry) and 5.60 mL (23 mmol) of 4 - n - octylstyrene (Tokyo Chemical Industry) were added to a 100 mL two - necked flask, and the mixture was stirred at 0 °C for 1 hour and at room temperature for 2 hours. Under ice cooling, 6.2 mL of water was added, and the mixture was stirred at room temperature for 2 hours. The resulting mixture was concentrated under reduced pressure, ethyl acetate and an aqueous sodium hydrogen carbonate solution were added, and the phases were separated. The organic phase was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to synthesize (4 - octylphenylethyl)boronic acid.

[0208] Under a nitrogen atmosphere, the obtained boronic acid was added to a 300 mL eggplant - shaped flask, 5.78 g (48.7 mmol) of pinacol (Tokyo Chemical Industry) and 40.0 mL of diethyl ether (Fuji Film Wako Pure Chemical Industries, dehydrated grade) were added, and the mixture was stirred at room temperature. 6.09 g (50.6 mmol) of magnesium sulfate (Fuji Film Wako Pure Chemical Industries) was added thereto, and the mixture was stirred at room temperature for 4 hours. The solid was filtered off by suction filtration under reduced pressure, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane) to obtain 2.40 g of a colorless liquid of 4,4,5,5 - tetramethyl - 2 - (4 - octylphenylethyl) - 1,3,2 - dioxaborolane (yield 29%).

[0209] 1 H NMR (CDCl3): δ = 7.12 (d, J = 8.1 Hz, 2H), 7.07 (d, J = 8.1 Hz, 2H), 2.72 (t, J = 8.1 Hz, 2H), 2.56 (t, J = 7.6 Hz, 2H), 1.62 - 1.55 (m, 2H), 1.34 - 1.26 (m, 10H), 1.23 (s, 12H), 1.14 (t, J = 8.3 Hz, 2H), 0.89 (t, J = 6.7 Hz, 3H). 4,4,5,5 - Tetramethyl - 2 - (4 - octylphenylethyl) - 1,3,2 - dioxaborolane

[0210]

Chem.

[0211] Synthesis Example 14 Synthesis of 2-(4-octylphenethyl)anthra[1,2-b:5,6-b']dithiophene Under a nitrogen atmosphere, 401 mg of 2-bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22 in the said publication) synthesized by the method described in WO2021 / 177417, 48.1 mg (0.214 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Corporation), 206 mg (0.441 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), and 397 mg (3.54 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL Schlenk tube. To this, a solution of 1.07 g (3.11 mmol) of 4,4,5,5-tetramethyl-2-(4-octylphenylethyl)-1,3,2-dioxaborolane synthesized in Synthesis Example 13 in 35.0 mL of toluene (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) and 3.0 mL of water were added, and the mixture was stirred at 80 °C for 19 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Corporation), and the resulting solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from toluene / heptane to obtain 189 mg of a yellow solid of 2-(4-octylphenethyl)anthra[1,2-b:5,6-b']dithiophene (yield 34%).

[0212] 11H NMR (CDCl3): δ = 8.70 (s, 1H), 8.62 (s, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 8.3 Hz, 1H), 7.82 (d, J = 8.7 Hz, 1H), 7.71 (d, J = 8.7 Hz, 1H), 7.54 (d, J = 5.0 Hz, 1H), 7.49 (d, J = 5.0 Hz, 1H), 7.20 - 7.12 (m, 5H), 3.32 (t, J = 7.8 Hz, 2H), 3.12 (t, J = 8.0 Hz, 2H), 2.59 (t, J = 7.8 Hz, 2H), 1.65 - 1.55 (m, 2H), 1.32 - 1.28 (m, 10H), 0.88 (t, J = 6.9 Hz, 3H). (2-(4-Octylphenethyl)anthra[1,2-b:5,6-b’]dithiophene)

[0213]

Chem.

[0214] Synthesis Example 15 2-Bromo-8-(4-octylphenethyl)[1,2-b:5,6-b’]dithiophene Under a nitrogen atmosphere, 126 mg (0.247 mmol) of 2-(4-octylphenethyl)anthra[1,2-b:5,6-b’]dithiophene synthesized in Synthesis Example 14 and 4.0 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, 0.540 mL (0.864 mmol) of 1.6 M n-butyllithium (FUJIFILM Wako Pure Chemical Industries) was added, and the mixture was stirred at -78 °C for 3 hours. 324 mg (0.995 mmol) of 1,2-dibromotetrachloroethane was added thereto at -78 °C, and the mixture was stirred while warming to room temperature. 1 M hydrochloric acid was added, the solid was filtered, washed with water and methanol, and 127 mg of a yellow solid of 2-bromo-8-(4-octylphenethyl)[1,2-b:5,6-b’]dithiophene was obtained (yield 73%).

[0215] 11H NMR (CDCl3): δ = 8.60 (s, 1H), 8.53 (s, 1H), 7.87 (d, J = 8.7 Hz, 1H), 7.85 (d, J = 8.2 Hz, 1H), 7.72 (d, J = 9.4 Hz, 1H), 7.69 (d, J = 9.1 Hz, 1H), 7.46 (s, 1H), 7.19 - 7.12 (m, 5H), 3.32 (t, J = 7.8 Hz, 2H), 3.11 (t, J = 7.8 Hz, 2H), 2.59 (t, J = 7.8 Hz, 2H), 1.65 - 1.58 (m, 2H), 1.32 - 1.28 (m, 10H), 0.88 (t, J = 6.9 Hz, 3H). (2-Bromo-8-(4-octylphenethyl)[1,2-b:5,6-b’]dithiophene)

[0216]

Chem.

[0217] Example 8 Synthesis of 2-Hexyl-8-(4-octylphenethyl)anthra[1,2-b:5,6-b’]dithiophene (Compound 8) Under a nitrogen atmosphere, 60.7 mg (0.0777 mmol) of 2-bromo-8-(4-octylphenethyl)[1,2-b:5,6-b’]dithiophene synthesized in Synthesis Example 15, 6.0 mg (0.027 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Industries, Ltd.), 25.8 mg (0.0553 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), 38.0 mg (0.339 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.), and 29.6 mg (0.228 mmol) of hexylboronic acid (Tokyo Chemical Industry Co., Ltd.) were added to a 50 mL Schlenk tube. 5.0 mL of toluene (FUJIFILM Wako Pure Chemical Industries, Ltd., dehydrated grade) and 1.0 mL of water were added, and the mixture was stirred at 80 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Industries, Ltd.), and the obtained solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 24.1 mg of a yellow solid of 2-hexyl-8-(4-octylphenethyl)anthra[1,2-b:5,6-b’]dithiophene (Compound 8) (yield 52%).

[0218] 1 1H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.8 Hz, 1H), 7.84 (d, J = 8.8 Hz, 1H), 7.71 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.9 Hz, 1H), 7.20 - 7.12 (m, 6H), 3.32 (t, J = 8.0 Hz, 2H), 3.12 (t, J = 8.0 Hz, 2H), 3.01 (t, J = 7.5 Hz, 2H), 2.59 (t, J = 7.5 Hz, 2H), 1.87 - 1.79 (m, 2H), 1.65 - 1.58 (m, 2H), 1.50 - 1.43 (m, 2H), 1.38 - 1.28 (m, 14H), 0.93 - 0.87 (m, 6H).

[0219] Melting point: 147 °C (Compound 8)

[0220]

Chemical Structure

[0221] Example 9 Synthesis of 2-octyl-8-(4-octylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 9) Under a nitrogen atmosphere, 63.0 mg (0.0807 mmol) of 2-bromo-8-(4-octylphenethyl)[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 15, 5.40 mg (0.0241 mmol) of palladium(II) acetate (FUJIFILM Wako Pure Chemical Corporation), 23.1 mg (0.0495 mmol) of Ruphos (Tokyo Chemical Industry Co., Ltd.), 40.8 mg (0.364 mmol) of potassium tert-butoxide (Tokyo Chemical Industry Co., Ltd.), and 45.1 mg (0.285 mmol) of octylboronic acid (Tokyo Chemical Industry Co., Ltd.) were added to a 50 mL Schlenk tube. 5.0 mL of toluene (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) and 1.0 mL of water were added, and the mixture was stirred at 80 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, insoluble matters were removed using diatomaceous earth (FUJIFILM Wako Pure Chemical Corporation), and the obtained solution was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; toluene / hexane = 1 / 2). The obtained solid was purified by recycled HPLC and recrystallized from heptane to obtain 29.0 mg of a yellow solid of 2-octyl-8-(4-octylphenethyl)anthra[1,2-b:5,6-b']dithiophene (Compound 9) (yield 58%).

[0222] 1 H NMR (CDCl3): δ = 8.59 (s, 2H), 7.85 (d, J = 8.8 Hz, 1H), 7.84 (d, J = 8.8 Hz, 1H), 7.71 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.19 - 7.12 (m, 6H), 3.31 (t, J = 8.0 Hz, 2H), 3.11 (t, J = 8.0 Hz, 2H), 3.01 (t, J = 7.5 Hz, 2H), 2.59 (t, J = 7.5 Hz, 2H), 1.86 - 1.79 (m, 2H), 1.63 - 1.58 (m, 2H), 1.49 - 1.27 (m, 20H), 0.91 - 0.87 (m, 6H).

[0223] Melting point: 144 °C (Compound 9)

[0224]

Chem.

[0225] <Evaluation of Solubility and Heat Resistance> Toluene was added to the aromatic compounds obtained in Examples 4 to 9 to obtain a film-forming composition, and the weight of each organic solvent required to completely dissolve the aromatic compound at room temperature (25 °C) was measured. When the solubility (wt%) was calculated, it was confirmed to be 1.0 wt% or more. The determination at the point of complete dissolution was confirmed visually. Table 1 shows the solubility and melting point of the evaluated aromatic compounds. It was confirmed that all the compounds had high solubility and heat resistance.

[0226]

Table 1

[0227] Example 10 (Preparation of Solution for Forming Organic Semiconductor Layer, Organic Semiconductor Layer, and Organic Thin-Film Transistor) Under air, 1.74 mg of 2-(4-n-butylphenethyl)-8-hexylanthra[1,2-b:5,6-b']dithiophene (Compound 4) synthesized in Example 4 and 868 mg of toluene (FUJIFILM Wako Pure Chemical Industries, Pure Grade) were added to a 10 ml sample tube. After heating and dissolving at 50 °C, it was cooled to room temperature (25 °C) to prepare a solution for forming an organic semiconductor layer. The solution state was maintained even after 10 hours at 25 °C (the concentration of Compound 4 was 0.20 wt%), and it was confirmed that it was a compound suitable for film formation by drop casting and inkjet.

[0228] Using the obtained solution for forming an organic semiconductor layer, a bottom-gate-bottom-contact type p-type organic thin-film transistor was fabricated. Table 2 shows the materials and film-forming methods of each component member.

[0229]

Table 2

[0230] As a result of evaluating the transfer characteristics of the transistor element, the hole carrier mobility was 1.26 cm 2 / V·sec, and the threshold voltage was 0.64 V.

[0231] Examples 11 to 15 (Preparation of Solution for Forming Organic Semiconductor Layer, Organic Semiconductor Layer, and Organic Thin Film Transistor) A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 11, except that Compounds 5 to 9 synthesized in Examples 5 to 9 were used instead of Compound 4. The solution state was maintained even after 10 hours at 25 °C (the concentrations of Compounds 5 to 9 were 0.20% by weight), and it was confirmed that the compounds were suitable for film formation by drop casting and inkjet.

[0232] Using the obtained solution for forming an organic semiconductor layer, a bottom gate-bottom contact type p-type organic thin film transistor was fabricated using the materials and film formation methods of each constituent member shown in Table 2.

[0233] Table 3 shows the results of evaluating the transfer characteristics of the transistor element. It was found that all the compounds had high hole carrier mobility and low threshold voltage.

[0234]

Table 3

[0235] Comparative Example 1 (Preparation of Solution for Forming Organic Semiconductor Layer) Under air, 0.44 mg of 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (Sigma-Aldrich) and 434 mg of toluene (Fuji Film 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). It was confirmed that a solid had precipitated, and it was confirmed that the compound was unsuitable for film formation by drop casting and inkjet due to its low solubility.

[0236] Comparative Example 2 (Preparation of Solution for Forming Organic Semiconductor Layer) Under air, in a 10 ml sample tube, using 2,8-dioctylanthra[1,2-b:5,6-b']dithiophene synthesized by the method described in WO2021 / 177417, a solution for forming an organic semiconductor layer was prepared in the same manner as in Example 10. The solution remained in a liquid state even after 10 hours at 25 °C (0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet printing.

[0237] (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Using the solution for forming the organic semiconductor layer, the materials of each component member shown in Table 2 and the film formation method were used. However, a thin film was not formed, and a bottom-gate-bottom-contact type p-type organic thin film transistor could not be fabricated.

[0238] Comparative Example 3 (Preparation of Solution for Forming Organic Semiconductor Layer) Under air, in a 10 ml sample tube, using 2,7-bis(2-(4-heptylphenyl)ethyl)dithieno[3,2-b:2',3'-d]biphenylene (Compound 6 in the publication) synthesized by the method described in WO2021 / 177417, a solution for forming an organic semiconductor layer was prepared in the same manner as in Example 11. The solution remained in a liquid state even after 10 hours at 25 °C (0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet printing.

[0239] (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Using the solution for forming the organic semiconductor layer, a bottom-gate-bottom-contact type p-type organic thin film transistor was fabricated using the materials of each component member shown in Table 2 and the film formation method.

[0240] As a result of evaluating the transfer characteristics of the transistor element, the hole carrier mobility was 1.19 cm 2 / V·sec, and the threshold voltage was 5.26 V, confirming that the threshold voltage was high.

Industrial Applicability

[0241] The aromatic compound of the present invention can provide high carrier mobility and low threshold voltage, and is excellent in heat resistance and solubility, so it can be expected to be applied as a semiconductor device material typified by organic thin film transistors.

Explanation of reference numerals

[0242] (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: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims

Claim 1 An aromatic compound represented by any one of the following formulas (1-I) or (1-II). 【Chemical 1】 [(Here, X １ , X ２ each independently represents an oxygen atom, a sulfur atom, a selenium atom, or NR ９ . Y １ , Y ２ each independently represents CR １０ or a nitrogen atom. R ２ to R ４ , R ６ to R １０ each independently represents 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 R ５ represents a linear alkyl group having 1 to 20 carbon atoms, and R １ is a group represented by the following formula (2).)] [Chemical Formula 2] (Here, l and m each independently represent 0 or 1, and n represents an integer from 1 to 20. R １１ ~ R １５ each independently represents 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 at least one of R １１ ~ R １５ is a linear alkyl group having 1 to 20 carbon atoms.) ]] Claim 2 The aromatic compound according to Claim 1, which is represented by the compound represented by the formula (1-I). Claim 3 In the aromatic compound represented by the formula (1-I) or (1-II), R ２ ~R ４ , R ６ ~R １０ The aromatic compound according to claim 1, wherein is a hydrogen atom. Claim 4 In the aromatic compound represented by the formula (1-I), R ２ ~R ４ 、R ６ ~R １０ The aromatic compound according to claim 1, wherein is a hydrogen atom. Claim 5 In the aromatic compound represented by formula (1-I), R ２ ~R ４ 、R ６ ~R １２ 、R １４ 、R １５ is a hydrogen atom, and R １３ is a linear alkyl group having 1 to 20 carbon atoms. The aromatic compound according to claim 1. Claim 6 A solution for forming an organic semiconductor layer containing the aromatic compound according to any one of Claims 1 to 5. Claim 7 An organic semiconductor layer containing the aromatic compound according to any one of Claims 1 to 5. Claim 8 An organic thin film transistor containing the aromatic compound according to any one of Claims 1 to 5.

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