JP7159586B2 - Aromatic compounds, organic semiconductor layers, and organic thin film transistors - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel aromatic compounds that can be applied to electronic materials such as organic semiconductor materials, organic semiconductor layers using the same, and organic thin-film transistors. The present invention relates to a novel aromatic compound applicable to various device fabrication processes, an organic semiconductor layer using the same, and an organic thin film transistor.

BACKGROUND ART Organic semiconductor devices represented by organic thin film transistors have attracted attention in recent years because they have features that inorganic semiconductor devices do not have, such as energy saving, low cost, and flexibility. This organic semiconductor device is composed of several kinds of materials such as an organic semiconductor layer, a substrate, an insulating layer, an electrode, etc. Among them, the organic semiconductor layer responsible for charge carrier movement plays a central role in the device. Since the performance of an organic semiconductor device depends on the carrier mobility of the organic semiconductor material that constitutes the organic semiconductor layer, there is a demand for an organic semiconductor material that provides high carrier mobility.

Generally known methods for producing an organic semiconductor layer include a vacuum vapor deposition 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. It is Of these, the coating method can be carried out using printing technology without using high-temperature and high-vacuum conditions, so it can be expected to significantly reduce the manufacturing cost of device fabrication, and is an economically preferable process. is.

The organic semiconductor material used in such a coating method should have heat resistance of 130° C. or higher and a solubility of 0.1% by weight or higher at room temperature from the viewpoint of high carrier mobility and device fabrication processes. is preferred. Further, from the device point of view, it is preferable that the HOMO level is -5.4 eV or more and close to the work function of the electrode in order to reduce the contact resistance with the electrode.

Here, it is generally known that a low-molecular-weight semiconductor having a condensed-ring rod-like molecular long axis tends to exhibit high carrier mobility because of its higher crystallinity than a polymer semiconductor. However, when the number of condensed rings is 5 or less, there is a problem of a low melting point and a low HOMO level, and when the number of condensed rings is 6 or more, there is a problem of low solubility. At present, almost no low-molecular-weight organic semiconductor materials having a HOMO level are known.

At present, low-molecular-weight materials include 2,7-dialkyl-substituted benzothienobenzothiophenes (condensed 4-ring) (see, for example, Patent Document 1 and Non-Patent Document 1), 6,6′-dialkyldinaphthothienothiophenes ( Condensed 6 rings) (see, for example, Patent Document 2), terphenylene derivatives (see, for example, Patent Document 3), and the like have been proposed.

However, in the case of the dialkyl-substituted benzothienobenzothiophenes described in Patent Document 1 and Non-Patent Document 1, the HOMO level is -5.5 eV, and an improvement in the HOMO level has been desired. Moreover, there is a problem that the transistor operation is lost when heated to 130° C. or higher.

The 6,6'-dialkyldinaphthothienothiophene described in Patent Document 2 has a low solubility of 0.08 g/L or less (0.01% by weight or less, toluene) at 60°C.

Furthermore, the terphenylene derivative described in Patent Document 3 has a highly linear condensed ring skeleton composed of a benzene ring and a cyclobutene ring, and thus has a problem of reduced solubility.

Also, a compound having a tetrathienobiphenylene skeleton has been reported, but since it has a structure close to a disk shape, it is structurally unsuitable for forming an organic semiconductor layer and is not suitable as an organic semiconductor material. (see Non-Patent Document 2).

WO2008/047896 WO2010/098372 WO2006/109569

Journal of American Chemical Society, 2007, Vol. 129, pp. 15732-15733 Journal of American Chemical Society, 2013, vol.135, pp.1731-1734

The present invention has been made in view of the above problems, and its object is to provide a novel coating-type organic semiconductor material having high carrier mobility, high heat resistance, suitable solubility, and a high HOMO level. It is in.

As a result of intensive studies to solve the above problems, the present inventors have found that a novel aromatic compound provides an organic semiconductor material with high carrier mobility, high heat resistance, suitable solubility and HOMO level. The headline led to the completion of the present invention.

That is, the present invention relates to an aromatic compound represented by the following general formula (1-I) or (1-II), an organic semiconductor layer, and an organic thin film transistor using the same.

(where A represents a covalent bond, oxygen, sulfur, selenium, NR ¹⁴ , or CR ¹⁵ =CR ¹⁶ , A ¹ represents CR ³ =CR ⁴ , oxygen, sulfur, or selenium, A ² represents CR ⁷ =CR ⁸ , oxygen, sulfur, or selenium, and A ³ represents CR ⁵ =CR ⁶ , oxygen, sulfur, or selenium.Among combinations of two adjacent R ¹ to R ⁸ , one set to Three pairs form a monocyclic to condensed 4-ring, and all the rings constituting the monocyclic to condensed ⁴ -ring are 4- to 6-membered rings. R ⁸ is each independently hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, alkadienyl group having 4 to 22 carbon atoms, carbon It represents an alkadiynyl group having a number of 4 to 22, or an aryl group having a carbon number of 4 to 26. R ¹⁴ to R ¹⁶ each independently represent hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. 20 alkenyl group, alkynyl group having 2 to 20 carbon atoms, alkadienyl group having 4 to 22 carbon atoms, alkadiynyl group having 4 to 22 carbon atoms, or aryl group having 4 to 26 carbon atoms.)
The present invention will be described in detail below.

The aromatic compound of the present invention is a derivative represented by the above general formula (1-I) or (1-II).

A in general formulas (1-I) and (1-II) represents a covalent bond, oxygen, sulfur, selenium, NR ¹⁴ or CR ¹⁵ =CR ¹⁶ , and due to the high mobility, covalent bond, oxygen, sulfur is preferred.

A ¹ in general formulas (1-I) and (1-II) represents CR ³ ═CR ⁴ , oxygen, sulfur, or selenium, preferably CR ³ ═CR ⁴ , sulfur for stability, and CR ³ =CR ⁴ is more preferred.

A ² in general formulas (1-I) and (1-II) represents CR ⁷ =CR ⁸ , oxygen, sulfur, or selenium, preferably CR ⁷ =CR ⁸ , sulfur for stability, CR ⁷ =CR ⁸ is more preferred.

A ³ in general formulas (1-I) and (1-II) represents CR ⁵ =CR ⁶ , oxygen, sulfur, or selenium, preferably CR ⁵ =CR ⁶ , sulfur for stability, CR ⁵ =CR ⁶ is more preferred.

In general formulas (1-I) and (1-II), among combinations of two adjacent R ¹ to R ⁸ , 1 to 3 pairs form a monocyclic to condensed 4-ring, and the monocyclic All rings constituting the condensed 4-ring are 4- to 6-membered rings. In the present invention, when one to three of the combinations consisting of two adjacent R ¹ to R ⁸ do not form a monocyclic to condensed 4-ring, or all constituting the monocyclic to condensed 4-ring When the ring is not a 4- to 6-membered ring, the crystallinity is lowered, which causes carrier transfer to be lowered.

Specific examples of the 4- to 6-membered ring include cyclobutene ring, thiophene ring, furan ring, selenophene ring, thiazole ring, oxazole ring, pyrrole ring, imidazole ring, benzene ring, pyridine ring and the like. A cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, and a benzene ring are preferred because of their high mobility. A 4- or 5-membered ring is preferred, and a cyclobutene ring, a thiophene ring, a furan ring, and a selenophene ring are more preferred because of their particularly high solubility.

On the other hand, in general formulas (1-I) and (1-II), R ¹ to R ⁸ which do not form the monocyclic to condensed 4-ring are each independently hydrogen, halogen, or C 1-20. an alkyl group having 2 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. indicates

Halogens for R ¹ to R ⁸ include, for example, fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable because they are stable.

Examples of alkyl groups having 1 to 20 carbon atoms in R ¹ to R ⁸ include 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- Linear, branched or cyclic alkyl groups such as octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl and cycloheptyl groups can be mentioned. Among them, an alkyl group having 1 to 14 carbon atoms is preferable because it becomes a biphenylene derivative that exhibits particularly high mobility and high solubility. a 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 having 1 to 14 carbon atoms; Straight chain alkyl groups are more preferred.

Examples of the alkenyl group having 2 to 20 carbon atoms in R ¹ to R ⁸ 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, cyclo hexenyl-1-group, cycloheptenyl-1-group and the like.

Examples of the alkynyl group having 2 to 20 carbon atoms in R ¹ to R ⁸ 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 and the like.

Examples of the alkadienyl group having 4 to 22 carbon atoms in R ¹ to R ⁸ include butadienyl group, pentadienyl group, hexadienyl group, n-heptadienyl group, n-octadienyl group, n-nonadienyl group, n-decadienyl group, n -dodecadienyl group, n-tridecadienyl group and the like, preferably an alka-1,3-dienyl group having 4 to 22 carbon atoms, hexa-1,3-dienyl group, n-hepta-1,3- A dienyl group, n-octa-1,3-dienyl group, n-nona-1,3-dienyl group and n-deca-1,3-dienyl group are more preferred.

Examples of the alkadiynyl group having 4 to 22 carbon atoms in R ¹ to R ⁸ include butadiynyl group, pentadiynyl group, hexadiynyl group, n-heptadynyl group, n-octadiynyl group, n-nonadynyl group, n-decadiynyl group, Examples include an n-dodecadiynyl group and an n-tridecadiynyl group, preferably a 1,3-alkadiynyl group having 4 to 22 carbon atoms, a hexa-1,3-diynyl group, an n-hepta-1,3- A diynyl group, n-octa-1,3-diynyl group, n-nona-1,3-diynyl group and n-deca-1,3-diynyl group are more preferred.

The aryl group having 4 to 26 carbon atoms in R ¹ to R ⁸ includes a heteroaryl group having 4 to 24 carbon atoms. The aryl group having 4 to 26 carbon atoms includes, for example, a phenyl group; p-tolyl group, p-(n-hexyl)phenyl group, p-(n-octyl)phenyl group, p-(2-ethylhexyl)phenyl Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5-(n- propyl)-2-furyl group, 5-(n-butyl)-2-furyl group, 5-(n-pentyl)-2-furyl group, 5-(n-hexyl)-2-furyl group, 5-( n-octyl)-2-furyl group, 5-(2-ethylhexyl)-2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-(n-propyl)-2-thienyl group, 5-(n-butyl)-2-thienyl group, 5-(n-pentyl)-2-thienyl group, 5-(n-hexyl)-2-thienyl 5-(n-octyl)-2-thienyl group, 5-(2-ethylhexyl)-2-thienyl group and other alkyl-substituted heteroaryl groups.

Among these R ¹ to R ⁸ , hydrogen, halogen, and an alkyl group having 1 to 20 carbon atoms are preferable because of high mobility, and hydrogen, fluorine, chlorine, methyl group, ethyl group, n-propyl group, n- A butyl group is more preferred, and hydrogen is particularly preferred.

In general formulas (1-I) and (1-II), R ¹⁴ to R ¹⁶ each independently represent hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, carbon It represents 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.

The halogen for R ¹⁴ to R ¹⁶ includes, for example, fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable because they are stable.

Examples of alkyl groups having 1 to 20 carbon atoms in R ¹⁴ to R ¹⁶ include 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- Linear, branched or cyclic alkyl groups such as octadecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl and cycloheptyl groups can be mentioned. Among them, an alkyl group having 1 to 14 carbon atoms is preferable because it becomes an aromatic compound exhibiting particularly high mobility and high solubility. -pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group and n-tetradecyl group having 1 to 14 carbon atoms Straight chain alkyl groups are more preferred.

Examples of the alkenyl group having 2 to 20 carbon atoms in R ¹⁴ to R ¹⁶ 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, cyclo hexenyl-1-group, cycloheptenyl-1-group and the like.

Examples of the alkynyl group having 2 to 20 carbon atoms in R ¹⁴ to R ¹⁶ 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 and the like.

Examples of the alkadienyl group having 4 to 22 carbon atoms in R ¹⁴ to R ¹⁶ include butadienyl group, pentadienyl group, hexadienyl group, n-heptadienyl group, n-octadienyl group, n-nonadienyl group, n-decadienyl group, n -dodecadienyl group, n-tridecadienyl group and the like, preferably an alka-1,3-dienyl group having 4 to 22 carbon atoms, hexa-1,3-dienyl group, n-hepta-1,3- A dienyl group, n-octa-1,3-dienyl group, n-nona-1,3-dienyl group and n-deca-1,3-dienyl group are more preferable.

Examples of the alkadiynyl group having 4 to 22 carbon atoms in R ¹⁴ to R ¹⁶ include butadiynyl group, pentadiynyl group, hexadiynyl group, n-heptadynyl group, n-octadiynyl group, n-nonadynyl group, n-decadiynyl group, Examples include an n-dodecadiynyl group and an n-tridecadiynyl group, preferably a 1,3-alkadiynyl group having 4 to 22 carbon atoms, a hexa-1,3-diynyl group, an n-hepta-1,3- A diynyl group, n-octa-1,3-diynyl group, n-nona-1,3-diynyl group and n-deca-1,3-diynyl group are more preferred.

The aryl group having 4 to 26 carbon atoms in R ¹⁴ to R ¹⁶ includes a heteroaryl group having 4 to 24 carbon atoms. The aryl group having 4 to 26 carbon atoms includes, for example, a phenyl group; p-tolyl group, p-(n-hexyl)phenyl group, p-(n-octyl)phenyl group, p-(2-ethylhexyl)phenyl Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5-(n- propyl)-2-furyl group, 5-(n-butyl)-2-furyl group, 5-(n-pentyl)-2-furyl group, 5-(n-hexyl)-2-furyl group, 5-( n-octyl)-2-furyl group, 5-(2-ethylhexyl)-2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-(n-propyl)-2-thienyl group, 5-(n-butyl)-2-thienyl group, 5-(n-pentyl)-2-thienyl group, 5-(n-hexyl)-2-thienyl 5-(n-octyl)-2-thienyl group, 5-(2-ethylhexyl)-2-thienyl group and other alkyl-substituted heteroaryl groups.

Among these R ¹⁴ to R ¹⁶ , hydrogen, halogen, and alkyl groups having 1 to 20 carbon atoms are preferred because of their high mobility.

The aromatic compound represented by the general formula (1-I) or (1-II) is preferably an aromatic compound represented by the following general formula (2) for ease of synthesis.

[(Here, among the combinations of two adjacent R ¹ to R ⁸ , 1 to 3 pairs form a monocyclic to condensed 4-ring represented by the following general formula (3), and the monocyclic to All the rings constituting the condensed 4 rings are 4- to 6-membered rings, and R ¹ to R ⁸ and A not forming the following general formula (3) are represented by the above general formulas (1-I), (1 have the same meanings as R ¹ to R ⁸ which do not form a monocyclic to condensed 4-ring group, and A in -II).)

(where X represents a covalent bond, oxygen, sulfur, selenium, CR ¹⁰ =C, or nitrogen, and Y represents carbon or nitrogen; l is 0 when X is a covalent bond, oxygen, sulfur, selenium; , X is CR ¹⁰ =C, 1 when X is nitrogen, m is 1 when Y is carbon, and 0 when Y is nitrogen, consisting of two adjacent R ⁹ to R ¹¹ and R ¹³ . One of the combinations may form a monocyclic to condensed three-ring represented by the following general formula (4), and all the rings constituting the monocyclic to condensed three-ring may be 4- to 6-membered rings. R ⁹ to R ¹¹ and R ¹³ that do not form the following general formula (4) are R ¹ to R ⁴ or R ⁵ to R ^8. When X is a covalent bond, A in general formula (2) is oxygen, sulfur, selenium, NR ¹⁴ or CR ¹⁵ =CR ¹⁶ , and X is oxygen, sulfur, selenium, CR ¹⁰ =C, or nitrogen, A in the general formula (2) is a covalent bond.When X is CR ¹⁰ =C, from two adjacent to form a six-membered ring The positions of such a combination are R ¹ and R ² , R ⁵ and R ^6. However, R ¹ to R ⁸ which do not form a monocyclic to condensed 4-ring, R which does not form the general formula (4) ⁹ to R ¹¹ and R ¹³ , and R ¹⁴ , R ¹⁵ and R ¹⁶ are simultaneously hydrogen.)

(where X ¹ represents a covalent bond, oxygen, sulfur, selenium, CR ¹⁸ =C, or nitrogen; Y ¹ represents carbon or nitrogen; n is X ¹ a covalent bond, oxygen, sulfur, or selenium); is 0 when X ¹ is CR ¹⁸ =C or nitrogen, o is 1 when Y ¹ is carbon, and 0 when Y ¹ is nitrogen, adjacent R ¹⁷ to R ²⁰ Of the combination consisting of two, one set constitutes the following general formula (5) or general formula (6), and can form a 4- to 6-membered ring.A in general formula (2) is a covalent bond , NR ¹⁴ , or CR ¹⁵ =CR ¹⁶ , R ¹⁷ to R ²⁰ not constituting general formula (5) or general formula (6) are represented by general formulas (1-I) and (1-II ) which does not form a monocyclic ring to condensed tetracyclic ring or R ⁵ to R ^{8. In} addition, when A in the general formula ( ² ) is oxygen, sulfur, or selenium , R ¹⁷ to R ²⁰ not constituting general formula (5) or general formula (6) are each independently hydrogen, methyl group, ethyl group, n-propyl group, alkyl group having 4 to 20 carbon atoms and only one is an alkyl group having 4 to 20 carbon atoms, provided that R ¹⁷ to R ²⁰ are both hydrogen.)

(Here, X ² represents oxygen, sulfur, selenium, CR ²² =CR ²³ or NR ²⁴ , Y ² represents CR ²⁵ or nitrogen. R ²¹ to R ²⁵ each independently represent hydrogen, halogen , an alkyl group having 1 to 20 carbon atoms, and at least one of R ²¹ to R ²⁵ is a halogen or an alkyl group having 1 to 20 carbon atoms.)

(Here, R ²⁶ represents an alkyl group having 1 to 20 carbon atoms.)]
In the general formula (2), one to three of the combinations of two adjacent R ¹ to R ⁸ form a monocyclic to condensed 4-ring represented by the general formula (3), All rings constituting monocyclic to condensed tetracyclic rings are 4- to 6-membered rings. Specific examples of the 4- to 6-membered ring include rings similar to the rings in (1-I) and (1-II) above. Preferred are cyclobutene ring, thiophene ring, furan ring and selenophene ring.

The combination of two adjacent R ¹ to R ⁴ among the R ¹ to R ⁸ facilitates the formation of monocyclic to condensed tetracyclic rings represented by general formula (3). , only R ¹ and R ² , only R ² and R ³ , only R ³ and R ⁴ , combinations of R ¹ and R ² and R ³ and R ⁴ are preferred. Of said R ¹ to R ⁸ , it consists of adjacent two of R ⁵ to R ⁸ . ^Preferred combinations are ^R5 and ^R6 alone, ^R6 and ^R7 alone, ^R5 and ^R6 , and ^R7 and R8.

In addition, among the R ¹ to R ⁸ , for high mobility, only one set out of the combination of two adjacent R ¹ to R ⁴ and two adjacent R ⁵ to R ⁸ It is preferable that only one of the combinations constitutes general formula (3). From the viewpoint of high heat resistance and high solubility, R ¹ and R ² and R ⁵ and R ⁶ constitute general formula (3), or R ² and R ³ and R ⁶ and R ⁷ are general formula (3) It is further preferable to configure

In general formula (2), all of R ¹ to R ⁸ , that is, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ form general formula (3). When all four adjacent groups form the general formula (3), the aromatic compound of the general formula (2) becomes disk-shaped, which may make it difficult to exhibit performance as an organic semiconductor material.

In general formula (2), R ¹ to R ⁸ and A that do not form general formula (3) form monocyclic to condensed 4 rings in general formulas (1-I) and (1-II) above. R ¹ to R ⁸ which did not have the same meaning as A, respectively.

In general formula (3) above, X represents a covalent bond, oxygen, sulfur, selenium, CR ¹⁰ =C, or nitrogen, and Y represents carbon or nitrogen. For high mobility it is preferred that X represents a covalent bond, oxygen, sulfur, selenium or CR ¹⁰ =C and Y is carbon, X represents oxygen, sulfur or selenium and Y is carbon is more preferable. Here, when R ² and R ³ and R ⁶ and R ⁷ in general formula (2) form general formula (3), X is preferably oxygen, sulfur, or selenium because of high solubility.

In general formula (3) above, l is 0 when X is a covalent bond, oxygen, sulfur or selenium, and is 1 when X is CR ¹⁰ =C and nitrogen. m is 1 when Y is carbon and 0 when Y is nitrogen.

In the general formula (3), one of the combinations of adjacent two of R ⁹ to R ¹¹ and R ¹³ forms a monocyclic to condensed tricyclic ring represented by the general formula (4), All the rings constituting the monocyclic ring to condensed tricyclic ring can be 4- to 6-membered rings. Examples of the 4- to 6-membered ring include cyclobutene ring, furan ring, thiophene ring, selenophene ring, thiazole ring, benzene ring, pyridine ring and the like. A furan ring, a thiophene ring, a selenophene ring, and a benzene ring are preferred. R ⁹ to R ¹¹ and R ¹³ that do not form general formula (4) are R ¹ to R ⁴ or groups similar to those of R ⁵ to R ⁸ .

In general formula (3) above, when X is a covalent bond, A in general formula (2) is oxygen, sulfur, selenium, NR ¹⁴ or CR ¹⁵ =CR ¹⁶ , and X is oxygen, sulfur, selenium, CR When ¹⁰ =C or nitrogen, A in general formula (2) is a covalent bond. That is, when X in general formula (3) is a covalent bond, A in general formula (2) is stable, so oxygen, sulfur, selenium, NR ¹⁴ , CR ¹⁵ =CR ¹⁶ is an organic semiconductor When X is oxygen, sulfur, selenium, CR ¹⁰ =C, or nitrogen, A in the general formula (2) is a covalent bond because of high mobility, which is suitable as an organic semiconductor material. become a thing.

In the general formula (3), when X is CR ¹⁰ =C, the positions of the combination of two adjacent groups forming a 6-membered ring are R ¹ and R ² , R ⁵ and R ⁶ . At this time, since it has a bent structure and is highly soluble, it is suitable as an organic semiconductor material.

In the above general formula (3), R ¹ to R ⁸ that do not form a monocyclic to condensed 4-ring, and R ⁹ to R ¹¹ and R ¹³ that do not form the general formula (4) are hydrogen at the same time. Except that At the same time, when hydrogen is excluded, it becomes highly soluble, making it suitable as an organic semiconductor material.

In general formula (4) above, X ¹ represents a covalent bond, oxygen, sulfur, selenium, CR ¹⁸ =C, or nitrogen, and Y ¹ represents carbon or nitrogen. X ¹ is preferably a covalent bond, oxygen, sulfur, selenium, CR ¹⁸ =C due to high mobility, and carbon is preferable for Y ¹ due to high mobility. In addition, when X in general formula (3) is a covalent bond, X ¹ in general formula (4) is preferably oxygen, sulfur, selenium, CR ¹⁸ =C, or nitrogen because of high stability, More preferred is CR ¹⁸ =C.

In general formula (4) above, n is 0 when X ¹ is a covalent bond, oxygen, sulfur, or selenium, and 1 when X ¹ is CR ¹⁸ =C, or nitrogen. o is ¹ when Y1 is carbon and ⁰ when Y1 is nitrogen.

In the above general formula (4), one of the combinations of two adjacent R ¹⁷ to R ²⁰ constitutes the above general formula (5) or general formula (6) to form a 4- to 6-membered ring can do. Examples of the 4- to 6-membered ring include benzocyclobutene ring, furan ring, thiophene ring, selenophene ring, thiazole ring, benzene ring, and pyridine ring. , furan ring, thiophene ring, selenophene ring and benzene ring are preferred.

In general formula (4) above, when A in general formula (2) is a covalent bond, NR ¹⁴ , or CR ¹⁵ =CR ¹⁶ , R ¹⁷ that did not constitute general formula (5) or general formula (6) to R ²⁰ represent the same groups as R ¹ to R ⁴ or R ⁵ to R ⁸ which did not form a monocyclic ring to condensed 4-ring in the general formulas (1-I) and (1-II). Among these, when R ¹⁷ to R ²⁰ are alkyl groups having 1 to 20 carbon atoms, alkyl groups having 4 to 14 carbon atoms are preferable because aromatic compounds exhibit particularly high mobility and high solubility. , n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group , and an n-tetradecyl group having 4 to 14 carbon atoms are more preferable. Note that R ¹⁷ to R ²⁰ not constituting general formula (5) or general formula (6) are preferably not hydrogen at the same time because of their high solubility.

When A in general formula (2) is oxygen, sulfur, or selenium, R ¹⁷ to R ²⁰ not constituting general formula (5) or general formula (6) are each independently hydrogen, methyl group , an ethyl group, an n-propyl group, and an alkyl group having 4 to 20 carbon atoms, only one of which is an alkyl group having 4 to 20 carbon atoms. At this time, since the mobility becomes high, it becomes suitable as an organic semiconductor material. Further, it is more preferable that only one of R ¹⁷ to R ²⁰ is an alkyl group having 4 to 14 carbon atoms.

In general formula (4) above, R ¹⁷ to R ²⁰ not constituting general formula (5) or general formula (6) are simultaneously hydrogen. At the same time, when hydrogen is excluded, it becomes highly soluble, making it suitable as an organic semiconductor material.

In the above general formula (5), X2 represents oxygen, sulfur, selenium, ^{CR22 = CR23} , or ^NR24 , and ^Y2 represents ^CR25 or nitrogen. X ² is preferably oxygen, sulfur, selenium, CR ²² =CR ²³ due to its high mobility and Y ¹ is preferably CR ²⁵ due to its high mobility.

In the above general formula (5), R ²¹ to R ²⁵ are each independently selected from the group consisting of hydrogen, halogen and alkyl groups having 1 to 20 carbon atoms, and one or more of R ²¹ to R ²⁵ is a halogen or an alkyl group having 1 to 20 carbon atoms. When at least one of R ²¹ to R ²⁵ is a halogen or an alkyl group having 1 to 20 carbon atoms, it is highly soluble and preferred.

The halogen is, for example, fluorine, chlorine, bromine or iodine, preferably fluorine and chlorine because they are stable.

Examples of the alkyl group having 1 to 20 carbon atoms of R ²¹ to R ²⁵ include the alkyl groups having 1 to 20 carbon atoms in R ¹ to R ⁸ of (1-I) and (1-II) above. Among them, an alkyl group having 4 to 14 carbon atoms is preferable because it becomes an aromatic compound that exhibits particularly high mobility and high solubility, n-butyl group, n-pentyl group, n-hexyl C 4-14 linear 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 More preferred are chain alkyl groups.

R ²⁶ in the general formula (6) represents an alkyl group having 1 to 20 carbon atoms, and since it becomes a biphenylene derivative exhibiting high mobility and high solubility, an alkyl group having 4 to 14 carbon atoms is preferable, n -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n A linear alkyl group having 4 to 14 carbon atoms, which is a -tetradecyl group, is more preferable.

In addition, the aromatic compound represented by the above general formula (1-I) or general formula (1-II) is also suitable as a biphenylene derivative represented by the following general formula (7).

[(Here, among combinations of two adjacent R ¹ to R ⁸ , 1 to 3 pairs constitute the following general formula (8) to form a 5- or 6-membered ring. The following general formula ( R ¹ to R ⁸ not constituting 8) are each independently hydrogen, halogen, 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, or an aryl group having 4 to 26 carbon atoms.)

(Here, X represents oxygen, sulfur, selenium, CR ¹⁰ =CR ¹¹ or NR ¹² , Y represents CR ¹³ or nitrogen. R ⁹ to R ¹³ are each independently hydrogen, halogen, carbon 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, or an aryl group having 4 to 26 carbon atoms.)]
In the general formula (7), 1 to 3 pairs of adjacent pairs of R ¹ to R ⁸ constitute the general formula (8) to form a 5- or 6-membered ring. Among the R ¹ to R ⁸ , the combination of ^two adjacent R ¹ to R ⁴ makes it easy to form the general ^formula (8). Combinations of ² and R3 only ^, R3 and ^R4 only ^{, R1} and ^R2 and R3 and ^{R4 are} preferred. Among the R ¹ to R ⁸ , the combination of R ⁵ to R ⁸ is preferably a combination of R ⁵ and R ⁶ alone, R ⁶ and R ⁷ alone, R ⁵ and R ⁶ and R ⁷ and R ⁸ .

R ¹ to R ⁸ that do not constitute the general formula (8) are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a It represents an alkynyl group or an aryl group having 4 to 26 carbon atoms.

In the above general formula (7), the halogen represented by R ¹ to R ⁸ is, for example, fluorine, chlorine, bromine, or iodine, and fluorine is preferable because of its stability.

In the above general formula (7), the alkyl group having 1 to 20 carbon atoms in R ¹ to R ⁸ is, for example, 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-dodecyl group, n-tetradecyl group, n-octadecyl group, 2 linear, branched or cyclic alkyl groups such as -ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group. Among them, an alkyl group having 1 to 14 carbon atoms is preferable because it becomes a biphenylene derivative that exhibits particularly high mobility and high solubility. a pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group and n-tetradecyl group, a linear alkyl group having 1 to 14 carbon atoms; More preferred.

In the above general formula (7), the alkenyl group having 2 to 20 carbon atoms in R ¹ to R ⁸ is, for example, ethenyl group, n-propenyl group, n-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 and the like.

In the above general formula (7), the alkynyl group having 2 to 20 carbon atoms in R ¹ to R ⁸ is, for example, ethynyl group, n-propynyl group, n-butynyl group, n-pentynyl group, n-hexynyl group, n -heptynyl group, n-octynyl group, n-nonynyl group, n-decynyl group, n-dodecynyl group and the like.

In general formula (7) above, the aryl group having 4 to 26 carbon atoms in R ¹ to R ⁸ includes a heteroaryl group having 4 to 24 carbon atoms. For example, phenyl group; p-tolyl group, p-(n-hexyl)phenyl group, p-(n-octyl)phenyl group, p-(2-ethylhexyl)phenyl group and other alkyl-substituted phenyl groups; 2-furyl group , 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5-(n-propyl)-2-furyl group, 5-(n -Butyl)-2-furyl group, 5-(n-pentyl)-2-furyl group, 5-(n-hexyl)-2-furyl group, 5-(n-octyl)-2-furyl group, 5- (2-ethylhexyl)-2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-(n-propyl)-2-thienyl group , 5-(n-butyl)-2-thienyl group, 5-(n-pentyl)-2-thienyl group, 5-(n-hexyl)-2-thienyl group, 5-(n-octyl)-2- Alkyl-substituted heteroaryl groups such as thienyl group and 5-(2-ethylhexyl)-2-thienyl group can be mentioned.

In the general formula (7), R ¹ to R ⁸ are preferably hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms because of their high mobility, such as hydrogen, fluorine, methyl group, ethyl group, n-propyl. more preferred is the n-butyl group, and particularly preferred is hydrogen.

Of the combinations of two adjacent R ¹ to R ⁸ in general formula (7), at least one pair constitutes general formula (8) and can form a 5- or 6-membered ring. Specific examples of the 5- or 6-membered ring include thiophene ring, furan ring, selenophene ring, thiazole ring, oxazole ring, pyrrole ring, imidazole ring, benzene ring, pyridine ring and the like. A ring, a furan ring, a selenophene ring, and a benzene ring are preferred. A five-membered ring is preferred, and a thiophene ring, a furan ring, and a selenophene ring are more preferred because of their particularly high solubility.

Of the combinations of two adjacent R ¹ to R ⁸ in general formula (7), 1 to 3 pairs can constitute the following general formula (8) to form a 5- or 6-membered ring. , for high mobility, only one set out of the combination of two adjacent R ¹ to R ⁴ and only one set out of the combination of two adjacent R ⁵ to R ⁸ have the general formula It is preferable to configure (8). From the viewpoint of high heat resistance and high solubility, R ¹ and R ² and R ⁵ and R ⁶ constitute general formula (8), or R ² and R ³ and R ⁶ and R ⁷ are general formula (2) It is further preferable to configure

X in the general formula (8) represents oxygen, sulfur, selenium, CR ¹⁰ =CR ¹¹ or NR ¹² , and Y represents CR ¹³ or nitrogen. For high mobility it is preferred that X represents oxygen, sulfur, selenium, or CR ¹⁰ =CR ¹¹ and Y is CR ¹³ , X represents oxygen, sulfur or selenium and Y is CR ¹³ is more preferable.

Here, when R ² and R ³ and R ⁶ and R ⁷ form the general formula (8), X is preferably oxygen, sulfur or selenium because of high solubility.

In general formula (7) above, all of R ¹ to R ⁸ , that is, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ and R ⁷ and R ⁸ constitute general formula (8) ( When all four adjacent pairs constitute the general formula (8), the biphenylene derivative of the general formula (7) has a disk shape. In order to obtain an organic semiconductor material with higher mobility and higher solubility, it is preferable not to have such a disk-shaped structure.

In general formula (8), R ⁹ to R ¹³ each independently represent hydrogen, halogen, 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, or an aryl group having 4 to 26 carbon atoms, but due to high solubility, R ⁹ is a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. , is preferably an aryl group having 4 to 26 carbon atoms. Examples of the halogen, alkyl group, alkenyl group, alkynyl group and aryl group include the groups represented by R ¹ to R ⁸ above.

In general formula (8), R ⁹ to R ¹³ are preferably hydrogen, halogen, or an alkyl group having 1 to 14 carbon atoms because of their high mobility. Hydrogen, fluorine, ethyl group, n-propyl group, n- propyl 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-dodecyl more preferred is the n-tetradecyl group.

In the general formula (8), as R ⁹ to R ¹³ , R ⁹ is an alkyl group having 1 to 14 carbon atoms, and R ¹⁰ to R ¹³ are hydrogen, fluorine, or methyl groups because of high mobility and high solubility. , ethyl group, n-propyl group and n-butyl group. Hydrogen is particularly preferred for R ¹⁰ -R ¹³ due to its high mobility.

More preferred specific skeletons of the aromatic compound of the present invention are represented by the following general formulas (1-1) to (1-33). Among these, from the viewpoint of high mobility, general formulas (1-1) to (1-5), (1-11) to (1-17), (1-21) to (1- 23), and (1-29) to (1-33) are preferred, and general formulas (1-1) to (1-3), (1-11) to (1-17), (1 -29) and (1-30) are more preferred.

(Here, R ¹ , R ³ to R ⁸ have the same meanings as R ¹ , R ³ to R ⁸ in general formulas (1-I) and (1-II), and X, Y, R ⁹ , R ¹³ and m have the same meanings as X, Y, R ⁹ , R ¹³ and m in general formula (3).)

(Here, R ³ , R ⁴ , R ⁷ and R ⁸ have the same meanings as R ³ , R ⁴ , R ⁷ and R ⁸ in general formulas (1-I) and (1-II), X has the same meaning as X in general formula (3), and X ¹ and R ¹⁷ have the same meaning as X ¹ and R ¹⁷ in general formula (4).)

(Here, A ¹ , R ¹ to R ⁸ have the same meanings as A ¹ , R ¹ to R ⁸ in general formulas (1-I) and (1-II), and R ¹⁰ , R ¹¹ and X are R ¹⁰ , R ¹¹ and X in general formula (3) have the same meanings, X ¹ and R ¹⁷ have the same meanings as X ¹ and R ¹⁷ in general formula (4), and X ² and R ²¹ , and R ²⁵ have the same meanings as X ² , R ²¹ and R ²⁵ in general formula (5).)

(Here, A ³ , R ¹ to R ⁴ have the same meanings as A ³ , R ¹ to R ⁴ in general formulas (1-I) and (1-II), and X, R ¹⁰ , R ¹¹ , R ¹³ and l have the same meanings as X, R ¹⁰ , R ¹¹ , R ¹³ and l in general formula (3), and X ¹ , R ¹⁹ and n are X ¹ and R shown in general formula (4). ¹⁹ and n, R ²¹ to R ²⁵ have the same meanings as R ²¹ to R ²⁵ in general formula (5), and R ²⁶ has the same meanings as R ²⁶ in general formula (6). show.)
Specific examples of the aromatic compound of the present invention include the following.

As the method for producing the aromatic compound of the present invention, any production method can be used as long as the aromatic compound can be produced.

As a method for producing the aromatic compound of the present invention, for example, R ³ , R ⁴ , R ⁷ and R ⁸ in general formula (2) are hydrogen, A is a covalent bond, and X in general formula (3) is The aromatic compound (1-1a) of general formula (1-1), wherein Y is carbon and R ¹³ is hydrogen, can be produced by the following steps A1 to E1.
(Step A1); In the presence of a palladium catalyst, 1-bromo-4-fluorophenyl-2-zinc chloride derived from 1-bromo-4-fluoro-2-iodobenzene and 2-bromo-4-fluoro- A step of producing 2,2′-dibromo-4,5′-difluorobiphenyl from 1-iodobenzene.
(Step B1); 2,2′-dibromo-4,5′-difluorobiphenyl obtained in Step A1 is treated with butyllithium to form a dilithium salt, and intramolecularly cyclized with copper(II) chloride to form a 2,6- A process for producing difluorobiphenylene.
(Step C1); The 2,6-difluorobiphenylene obtained in Step B1 is treated with lithium diisopropylamide (hereinafter abbreviated as LDA) and iodinated to produce 2,6-difluoro-1,5-dihalobiphenylene. process.
(Step D1); Sonogashira coupling of 2,6-difluoro-1,5-dihalobiphenylene obtained in Step C1 and an alkynyl compound in the presence of a palladium/copper catalyst to give 1,5-dialkynyl-2,6 - A process for producing difluorobiphenylene.
(Step E1); A step of reacting the 1,5-dialkynyl-2,6-difluorobiphenylene obtained in Step D1 with sodium sulfide to produce a biphenylene derivative (1-1a).

Details of each step are shown below.

The A1 step comprises 1-bromo-4-fluorophenyl-2-zinc chloride derived from 1-bromo-4-fluoro-2-iodobenzene and 2-bromo-4-fluoro- This is a step of producing 2,2'-dibromo-4,5'-difluorobiphenyl from cross-coupling of 1-iodobenzene.

1-bromo-4-fluorophenyl-2-zinc chloride can be prepared by converting iodine of 1-bromo-4-fluoro-2-iodobenzene into magnesium halide using an organometallic reagent such as ethylmagnesium chloride or isopropylmagnesium bromide. After exchange (preparation of 1-bromo-4-fluorophenyl-2-magnesium halide), it can be prepared by transmetallation with zinc chloride. It is also possible to use magnesium metal instead of the organometallic reagent.

Conditions for preparing 1-bromo-4-fluorophenyl-2-magnesium halide include, for example, tetrahydrofuran (hereinafter referred to as THF) or diethyl ether in a solvent such as -80°C to 20°C. can be implemented. 1-Bromo-4-fluorophenyl-2-zinc chloride can be prepared by reacting a solution of the magnesium salt (1-bromo-4-fluorophenyl-2-magnesium halide) with zinc chloride. Zinc chloride may be used as it is or may be in THF or diethyl ether solution. The reaction temperature between the magnesium salt and zinc chloride can be in the range of -80°C to 30°C.

Examples of the palladium catalyst in step A1 include tetrakis(triphenylphosphine)palladium and dichlorobis(triphenylphosphine)palladium, and the reaction temperature is in the range of 20°C to 80°C.

In step B1, 2,2'-dibromo-4,5'-difluorobiphenyl obtained in step A1 is converted to a dilithium salt with 2 equivalents or more of butyllithium, and intramolecularly cyclized with copper (II) chloride. This is the step of producing 2,6-difluorobiphenylene.

As conditions for preparing the dilithium salt, for example, 2 to 3 equivalents of n-butyllithium or tert-butyllithium are used in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. be able to.

Copper (II) chloride is used in an amount of 1-3 equivalents relative to the dilithium salt, and the intramolecular cyclization reaction can be carried out at a temperature range of -80°C to 30°C. Note that copper (II) bromide can be used instead of copper (II) chloride.

In the C1 step, the 2,6-difluorobiphenylene obtained in the B1 step is reacted with LDA to generate a dilithium salt at the 1- and 5-positions, and then halogenated to give 2,6-difluoro-1,5 - It is a process for producing dihalobiphenylenes.

As conditions for the reaction with LDA, for example, 2 to 4 equivalents of LDA can be used in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. The reaction between the dilithium salt and the halogenating agent can be carried out at -80°C to 30°C.

Instead of LDA, n-butyllithium, n-butyllithium/tetramethylethylenediamine can be used, and halogenating agents include iodine, 1-chloro-2-iodoethane, N-iodosuccinimide, bromotrichloromethane, tetra Halogenating agents such as bromomethane, 1,2-dibromotetrachloroethane, N-bromosuccinimide (hereinafter abbreviated as NBS), and N-fluorobenzenesulfonimide can be used.

In step D1, the 2,6-difluoro-1,5-dihalobiphenylene obtained in step C1 and an alkynyl compound undergo Sonogashira coupling in the presence of a palladium catalyst and a copper catalyst to give 1,5-dialkynyl-2, This is the step of producing 6-difluorobiphenylene.

Examples of the palladium catalyst in this case include tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, and the like. (I) etc. can be mentioned. Sonogashira coupling can be carried out in a solvent such as triethylamine, diisopropylamine, diisopropylethylamine, piperidine, pyridine, etc. at a temperature range of 20°C to 80°C. Toluene, THF, or the like may be added as a solvent.

Examples of alkynyl compounds in step D1 include 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1-decyne, 1-undecyne, and 1-dodecyne. mentioned.

The E1 step is a step of producing an aromatic compound (1-1a) by reacting the 1,5-dialkynyl-2,6-difluorobiphenylene obtained in the D1 step with sodium sulfide.

The reaction is carried out in a solvent such as dimethylsulfoxide (hereinafter abbreviated as DMSO), N,N-dimethylformamide (hereinafter abbreviated as DMF), N-methylpyrrolidone (hereinafter abbreviated as NMP), and the like. , 40-200°C.

This step can also be carried out using known reaction conditions for synthesizing a benzothiophene ring from 2-haloalkynylbenzene (eg, Organic Letters, 2009, 11, pp. 2473-2475).

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ⁹ has the same meaning as R ⁹ represented by general formula (3).)
On the other hand, among the aromatic compounds of the general formula (2) used in the present invention, R ³ , R ⁴ , R ⁷ and R ⁸ are hydrogen, A is a covalent bond, and X in the general formula (3) is sulfur. , Y is carbon, and R ¹³ is hydrogen, the aromatic compound (1-2a) of general formula (1-2) can be produced by the following steps A2 to E2.
(Step A2); In the presence of a palladium catalyst, 1-bromo-3-fluoro-2-iodobenzene-derived 1-bromo-3-fluorophenyl-2-zinc chloride and 2-bromo-1-fluoro- A step of producing 2,2′-dibromo-3,6′-difluorobiphenyl from 3-iodobenzene.
(Step B2); 2,2′-dibromo-3,6′-difluorobiphenyl obtained in Step A2 is treated with butyllithium to form a dilithium salt, and intramolecularly cyclized with copper(II) chloride to form a 1,5- A process for producing difluorobiphenylene.
(Step C2); A step of producing 1,5-difluoro-2,6-dihalobiphenylene by subjecting the 1,5-difluorobiphenylene obtained in step B2 to LDA treatment/halogenation.
(D2 step); Sonogashira coupling of 1,5-difluoro-2,6-dihalobiphenylene obtained in step C2 with an alkynyl compound in the presence of a palladium/copper catalyst to give 2,6-dialkynyl-1,5 - A process for producing difluorobiphenylene.
(Step E2); A step of reacting the 2,6-dialkynyl-1,5-difluorobiphenylene obtained in Step D2 with sodium sulfide to produce an aromatic compound (1-2a).

The steps A2 to E2 are the reagents of steps A1 to E1 above and the The aromatic compound represented by (1-2a) can be produced using reaction conditions and the like.

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ⁹ has the same meaning as R ⁹ represented by general formula (3).)
The biphenylene derivative (1-2a) in which R ⁹ is an alkyl group having 1 to 20 carbon atoms can be obtained by For example, it can be produced by a method including the following steps B3 to E3.
(Step B3); 2,2′-dibromo-3,6′-difluorobiphenyl obtained in Step A2 is dilithiated with butyllithium and reacted with N-fluorobenzenesulfonimide to give 1,5-difluorobiphenylene. manufacturing process.
(Step C3); 1,5-difluorobiphenylene obtained in Step B3 is reacted with sodium sulfide to form a dithiol, which is further reacted with 2-bromoacetaldehyde dimethylacetal to obtain biphenylene-1,5-bis(thioacetaldehyde dimethylacetal). ).
(Step D3); A step of cyclizing the biphenylene-1,5-bis(thioacetaldehyde dimethylacetal) obtained in Step C3 with a phosphoric acid catalyst to produce unsubstituted dithienobiphenylene.
(Step E3); A step of dilithiating the unsubstituted compound obtained in Step D3 by reacting it with n-butyllithium and treating it with an alkyl halide to produce an aromatic compound (1-2a).

In step B3, for example, 2,2′-dibromo-3,6′-difluorobiphenyl obtained in step A2 is dilithiated with 2 equivalents or more of butyllithium to generate benzyne for intramolecular cyclization to give N-fluoro A process for producing 1,5-difluorobiphenylene by fluorination with benzenesulfonimide.

As conditions for the dilithiation, for example, 2 to 3 equivalents of n-butyllithium or tert-butyllithium may be used in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. can. Fluorination with N-fluorobenzenesulfonimide can be carried out in a solvent such as THF or diethyl ether at temperatures ranging from -80°C to 20°C.

In step C3, for example, 1,5-difluorobiphenylene is reacted with 2 to 6 equivalents of sodium sulfide (hydrate) in a solvent such as DMF, NMP, etc. at 90°C to 150°C to obtain biphenylene-1,5. - dithiol disodium salt, add 2-bromoacetaldehyde dimethylacetal and treat at 90°C to 150°C.

In the D3 step, for example, biphenylene-1,5-bis(thioacetaldehyde dimethylacetal) obtained in the C3 step is treated with 5 to 20 mol% of a catalyst such as phosphoric acid or polyphosphoric acid in a solvent such as xylene or chlorobenzene. , 110-140°C.

In step E3, for example, the unsubstituted compound obtained in step D3 is reacted with 2 to 6 equivalents of n-butyllithium in a solvent such as THF at -10 to 65 ° C., and then 2 to 8 equivalents of alkyl halide. at -10 to 65°C. Thereby, the aromatic compound represented by (1-3a) can be produced.

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ⁹ represents an alkyl group having 1 to 20 carbon atoms.)
Furthermore, among the aromatic compounds of the general formula (2) used in the present invention, R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen, A is a covalent bond, and X in the general formula (3) is sulfur. , Y is carbon, and R ¹³ is hydrogen, the aromatic compound (1-3a) of the general formula (1-3) is obtained by using the 2,6-difluorobiphenylene obtained in the above A1 and B1 steps as a raw material, the following C4- It can be produced by a method that includes the steps of E4.
(Step C4); Halogenating the 2,6-difluorobiphenylene obtained in Step B1 to produce 2,6-dihalo-3,7-difluorobiphenylene.
(D4 step); Sonogashira coupling of 2,6-dihalo-3,7-difluorobiphenylene obtained in step C4 with an alkynyl compound in the presence of a palladium/copper catalyst to give 2,6-dialkynyl-3,7- A process for producing difluorobiphenylene.
(Step E4); A step of reacting the 2,6-dialkynyl-3,7-difluorobiphenylene obtained in Step D4 with sodium sulfide to produce an aromatic compound (1-3a).

In the C4 step in the reaction step, for example, the 2,6-difluorobiphenylene obtained in the B1 step is reacted with a halogenating agent to halogenate the 3- and 7-positions to give 2,6-dihalo-3,7 - It is a process for producing difluorobiphenylene.

As conditions for the reaction with the halogenating agent, for example, 2 to 4 equivalents of the halogenating agent can be used in a solvent such as DMF, NMP or DMSO at a temperature of 20°C to 70°C.

Halogenating agents such as NBS, bromine, iodine and N-iodosuccinimide can be used.

In steps D4 and E4, the reagents and reaction conditions of steps D1 and E1 above are used, except that 2,6-dihalo-3,7-difluorobiphenylene is used in step D4, and (1-3a) is The aromatic compounds shown can be prepared.

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ⁹ has the same meaning as R ⁹ represented by general formula (3).)
On the other hand, the aromatic compound represented by the above general formula (1-11) can be produced, for example, using the 2,6-difluoro-1,5-diiodobiphenylene obtained in the above (Step C1). .

Of the general formula (1-11), the aromatic compound (1-11a) in which R ³ , R ⁴ , R ⁷ and R ⁸ are hydrogen and X and X ¹ are sulfur can be prepared by following steps D5 to F5. It can be manufactured by a method that goes through.
(D5 step); 3-chlorothienyl-2-zinc chloride derived from 2-bromo-3-chlorothiophene and 2,6-difluoro-1,5-diiodobiphenylene in the presence of a palladium catalyst to give 2, A step of producing 6-difluoro-1,5-bis(3-chloro-2-thienyl)biphenylene.
(E5 step); 2,6-difluoro-1,5-bis(3-chloro-2-thienyl)biphenylene obtained in step D5 and sodium sulfide are subjected to a reaction to obtain unsubstituted bis(dithieno)biphenylene. manufacturing process.
(Step F5): A step of dilithiating the unsubstituted compound obtained in Step E5 by reacting it with n-butyllithium and treating it with an alkyl halide to produce an aromatic compound (1-11a).

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms.)
Further, the aromatic compound represented by the above general formula (1-16) can be produced, for example, using the 2,6-dibromo-3,7-difluorobiphenylene obtained in the above (Step C4).

Of the general formula (1-16), the aromatic compound (1-16a) in which R ³ and R ⁷ are fluorine, R ⁴ and R ⁸ are hydrogen, and X ¹ is sulfur, can be obtained by following steps D6 to F6. It can be manufactured by a method through
(Step D6); 5-alkyl-3-bromothienyl-2-zinc chloride derived from 5-alkyl-2,3-dibromothiophene and 2,6-dibromo-3,7- A step of producing 2,6-difluoro-3,7-bis(5-alkyl-3-bromo-2-thienyl)biphenylene from difluorobiphenylene.
(Step E6); Sonogashira of 2,6-difluoro-3,7-bis(5-alkyl-3-bromo-2-thienyl)biphenylene and trimethylsilylacetylene obtained by Step D6 in the presence of a palladium/copper catalyst. 2,6-difluoro-3,7-bis(5-alkyl-3-(trimethylsilylethynyl)-2-thienyl)biphenylene is produced by coupling, detrimethylsilylated by dilute hydrochloric acid treatment, and 2,6-difluoro-3, A process for producing 7-bis(5-alkyl-3-ethynyl-2-thienyl)biphenylene.
(F6 step); 2,6-difluoro-3,7-bis(5-alkyl-3-ethynyl-2-thienyl)biphenylene obtained in step E6 is subjected to a cyclization reaction in the presence of a ruthenium catalyst or platinum catalyst. and producing an unsubstituted biphenylene derivative (1-16a)bis(dithieno)biphenylene.

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms.)
The aromatic compound represented by the general formula (1-21) is, for example, in the general formula (1-21), R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen, X ¹ is CH═C, The aromatic compound (1-21a) in which R ¹⁹ is hydrogen can be produced by a method comprising steps A7 to F7 below.
(Step A7); 4-alkyl-2-bromo-phenyl-2-zinc chloride derived from 4-alkyl-2-bromo-1-iodobenzene and 2-bromo-4-fluoro in the presence of a palladium catalyst - A step of producing 4-alkyl-2,2'-dibromo-4'-fluorobiphenyl from 1-iodobenzene.
(Step B7); The 4-alkyl-2,2′-dibromo-4′-fluorobiphenyl obtained in Step A7 is converted to a dilithium salt with butyllithium, and intramolecularly cyclized with copper(II) chloride to give 2- A process for producing alkyl-7-fluorobiphenylene.
(C7 step): Halogenating the 2-alkyl-7-fluorobiphenylene obtained in step B7 to produce 2-alkyl-3,6-dihalo-7-fluorobiphenylene.
(Step D7); The 2-alkyl-3,6-dihalo-7-fluorobiphenylene obtained in Step C7 is monometallated with isopropyl Grignard and homocoupled with copper (II) chloride to give a bi(3-fluoro -6-alkyl-7-bromo-2-biphenylenyl).
(Step E7); Bi(3-fluoro-6-alkyl-7-bromo-2-biphenylenyl) obtained in Step D7 is dilithiated with butyllithium and protonated with methanol to give bi(3-fluoro-6). -alkyl-2-biphenylenyl).
(Step F7); A step of reacting bi(3-fluoro-6-alkyl-2-biphenylenyl) obtained in Step E7 with sodium sulfide to produce aromatic compound (1-21a).

For the conditions of each step, for example, the conditions listed above can be used.

The following reaction scheme shows a more specific production method, which is preferable because the number of reaction steps is small.

(Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms.)
Furthermore, the produced aromatic compound can be purified by subjecting it to column chromatography or the like, in which case the separating agent is, for example, silica gel or activated alumina, and the solvent is hexane, heptane, toluene, dichloromethane, Chloroform etc. can be mentioned.

The produced aromatic compound can be decolorized and purified in a solution by subjecting it to activated carbon, zeolite, activated alumina, etc. Examples of the solvent in that case include hexane, heptane, toluene, dichloromethane, and chloroform. .

In addition, the produced aromatic compound may be further purified by recrystallization, and the purity can be improved by increasing the number of recrystallizations. The number of times of recrystallization is preferably 2 to 5 from the viewpoint of high purity and high yield. The purity can be improved by increasing the number of times of recrystallization. Solvents used for recrystallization include, for example, hexane, heptane, octane, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene and the like, and mixtures of these in any ratio may be used.

In the recrystallization method, a solution of the aromatic compound is prepared by heating (the concentration of the solution at that time is preferably in the range of 0.01 to 10.0% by weight in order to efficiently remove impurities, and 0.05 to The range of 5.0% by weight is more preferable.), and the solution is cooled to precipitate and isolate crystals of the aromatic compound. Therefore, it is preferably in the range of -20°C to 40°C. In addition, it is possible to analyze by liquid chromatography when measuring the purity.

As a method for producing the aromatic compound of the present invention, a compound represented by the following general formula (10-I) or (10-II) is reacted with a straight-chain alkyllithium to obtain the following general formula (9-I) or ( It may be a method for producing an aromatic compound shown in 9-II).

(Here, A, A ¹ to A ³ , R ¹ , R ² and R ⁵ to R ⁸ are A, A ¹ to A ³ , have the same meanings as R ¹ , R ² , and R ⁵ to R ^8. )

^{( Here ,} X ³ and X ^{4 each} independently represent ^{a halogen} . have the same meanings as A, A ¹ to A ³ , R ¹ , R ² , and R ⁵ to R ⁸ in (1-II).)
The above manufacturing method will be described in detail below.

A in the above general formulas (9-I), (9-II), (10-I) and (10-II) is a covalent bond, oxygen, sulfur, selenium, NR ¹⁴ or CR ¹⁵ =CR ¹⁶ Covalent bonding is preferred because of the high yield of the reaction and the high yield of the reaction.

A ¹ is CR ³ =CR ⁴ , oxygen, sulfur or selenium, A ² is CR ⁷ =CR ⁸ , oxygen, sulfur or selenium, A ³ is CR ⁵ =CR ⁶ , oxygen, sulfur or selenium , Since the reaction proceeds easily, it is preferable that A ¹ is CR ³ = CR ⁴ and sulfur, A ² is CR ⁷ = CR ⁸ and sulfur, A ³ is CR ⁵ = CR ⁶ and sulfur, and A ¹ is More preferably, CR ³ =CR ⁴ , A ² is CR ⁷ =CR ⁸ and A ³ is CR ⁵ =CR ⁶ .

The halogen in X ³ and X ⁴ is, for example, fluorine, chlorine, bromine, or iodine, and X ³ is preferably fluorine, chlorine, or bromine, since the reactive intermediate benzyne is stably generated, and X ⁴ is Bromine is preferred.

R ¹ is preferably halogen or hydrogen, more preferably bromine or hydrogen, because it readily generates a reactive intermediate, benzyne.

Linear alkyllithium to be reacted with the compound represented by the general formula (10-I) or (10-II) includes, for example, n-butyllithium, methyllithium, n-propyllithium, n-pentyllithium, n- Examples include hexyllithium, n-heptyllithium, n-octyllithium, n-nonyllithium, n-decyllithium, and n-butyllithium is preferred because of its good availability.

The straight-chain alkyllithium reacts with the compound represented by the general formula (10-I) or (10-II) to produce a dilithium salt of the compound. A range of .0 equivalents is used, but 2.2 to 6.0 equivalents are preferred for high yields.

The reaction is carried out in a solvent, and the solvent is not particularly limited as long as the dilithium salt of the compound can stably exist. Ether solvents such as ether, tert-butyl ethyl ether, dimethoxyethane, dimethoxypropane and dioxane are preferred, and THF is more preferred.

The temperature of the reaction is, for example, −80° C. to 40° C., preferably −70° C. to 20° C., since benzyne, which is a reactive intermediate, is likely to be generated.

As a method for producing the aromatic compound of the present invention, a compound represented by the following general formula (12-I) or (12-II) is used, and a compound represented by the following general formula (11-I) or (11-II) is used. It may be a production method for producing an aromatic compound.

(Here, A ¹ , R ¹ , R ² and R ⁵ to R ⁸ are A ¹ , R ¹ , R ² and R ⁵ to R in general formulas (1-I) and (1-II) above. ^8. R ¹⁰ and R ¹¹ have the same meanings as R ¹⁰ and R ¹¹ in general formula (3) above, and R ²¹ and R ²⁵ have the same meanings as X ² and R in general formula (5) above. ²¹ and have the same meaning as R ^25. )

(Here, X ³ and X ⁴ each independently represent halogen, A ¹ , R ¹ , R ² , R ⁵ to R ⁸ , R ¹⁰ , R ¹¹ , X ² , R ²¹ and R ²⁵ are the same as A ¹ , R ¹ , R ² , R ⁵ to R ⁸ , R ¹⁰ , R ¹¹ , X ² , R ²¹ and R ²⁵ in the general formulas (11-I) and (11-II) indicate significance.)
A ¹ in the general formulas (11-I), (11-II), (12-I), and (12-II) is CR ³ =CR ⁴ and sulfur because the reaction proceeds easily. is preferred, and more preferably CR ³ =CR ⁴ . X ² is preferably CR ²² =CR ²³ and sulfur, more preferably CR ²² =CR ²³ , since the reaction proceeds easily.

R ¹ , R ⁸ , R ¹¹ , and R ²⁵ are preferably halogen or hydrogen, more preferably bromine or hydrogen, because they readily generate benzyne, which is a reactive intermediate.

When the compound represented by general formula (12-I) or (12-II) is reacted with straight-chain alkyllithium, the straight-chain alkyllithium gives a high yield with respect to the compound, so 3.5 to It is preferably used in the range of 6.5 equivalents, more preferably 3.8 to 6.0 equivalents.

The aromatic compound of the present invention can be made into an organic semiconductor layer forming solution containing the aromatic compound by dissolving it in an appropriate solvent. As the solvent, any solvent may be used as long as it is a solvent capable of dissolving the aromatic compound represented by the general formula (1). An organic solvent having a boiling point of 100° C. or higher at normal pressure is preferable.

Solvents that can be used in the present invention are not particularly limited. group hydrocarbons; anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethylphenyl ether, butylphenyl ether, 1,2- aromatic ethers such as methylenedioxybenzene and 1,2-ethylenedioxybenzene; chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-difluorobenzene, Aromatic halogen compounds such as 1,3-difluorobenzene and 1,4-difluorobenzene; 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, benzo heteroaromatics such as oxazole and pyridine; saturated hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane and decalin; 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 Glycols such as monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; dimethyl phthalate, diethyl phthalate, dimethyl terephthalate, phenyl acetate, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydro esters such as drofurfuryl propionate and γ-butyrolactone; and cyclic ethers such as THF and 2-methoxymethyltetrahydrofuran. - 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, ethylphenyl ether, butylphenyl ether, 1,2-methylenedioxybenzene, 1,2-ethylenedioxybenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1 , 4-dichlorobenzene, 3-methylthiophene, benzothiazole, more preferably toluene, o-xylene, mesitylene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole and 2,6-dimethylanisole.

As the solvent used in the present invention, one type of solvent can be used alone, or two or more types of solvents having different properties such as boiling points, polarities, and solubility parameters can be used in combination.

The temperature at which the aromatic compound represented by the general formula (1) is mixed and dissolved in the solvent is preferably in the temperature range of 0 to 80 ° C. for the purpose of promoting dissolution, and the temperature is 10 to 60 ° C. It is more preferable to carry out in the range.

The time for dissolving and mixing the aromatic compound represented by the general formula (1) in the organic solvent is preferably 1 minute to 1 hour in order to obtain a uniform solution.

In the present invention, when the concentration of the aromatic compound represented by the general formula (1) in the solution for forming an organic semiconductor layer of the present invention is in the range of 0.1 to 10.0% by weight, handling becomes easy, and the organic semiconductor layer is more efficient in forming the Moreover, when the viscosity of the organic semiconductor layer-forming solution is in the range of 0.3 to 10 mPa·s, more suitable coatability is exhibited.

The solution can be prepared at a relatively low temperature because the aromatic compound itself has moderate cohesiveness, and it has oxidation resistance, so it is suitable for the production of organic thin films by a coating method can. That is, the coating process can be simplified because there is no need to remove air from the atmosphere. Further, the solution is, 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-dimethyltriaryl amine), poly(N-vinylcarbazole), polymethyl methacrylate, poly(styrene-co-methyl methacrylate), polyethyl methacrylate, polyn-propyl methacrylate, polyisopropyl methacrylate, polyn-butyl methacrylate , polyphenyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyn-propyl acrylate, etc., preferably polystyrene, poly(α-methylstyrene), poly(ethylene-co-norbornene), A polymer such as polymethyl methacrylate can also be present as a binder. The concentration of these polymer binders is preferably 0.001 to 10.0% by weight for reasonable solution viscosity.

The glass transition temperature (Tg) of the polymer binder is preferably 105° C. or higher, more preferably 120° C. or higher, more preferably 150° C. or higher, because it is more suitable for handling process temperatures during electronic device production. is particularly preferred.

Further, the molecular weight of the polymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, since it is suitable for obtaining an organic thin film transistor having a higher carrier mobility. , 20,000 to 100,000 are particularly preferred. In the present invention, the molecular weight of the polymer refers to the weight average molecular weight (Mw) in terms of polystyrene.

The polymer has an effect as a general polymer binder and improves the film formability of the resulting organic semiconductor layer, and insulating polymers and semiconducting polymers can also be used.

Specific examples of polymers that can be used as the polymer binder in the present invention include, in addition to the polymers listed above, polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, and methyl methacrylate-styrene copolymers. Polymers etc. can be mentioned.

More specifically, the polar cyclic polyolefins are more preferably polymers represented by the following general formula (13).

(Here, R ²⁷ to R ²⁹ are each independently 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. , C7-20 aryloxycarbonyl group, cyano group, nitro group, C1-20 alkoxy group, C6-20 aryloxy group, hydroxyl group, amino group, or C1-20 represents an alkylamino group, X ³ is 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 is an integer of 20 to 5,000, q and r are each independently 0; represents an integer of ~2.A bond consisting of a solid line and a dotted line represents a single bond or a double bond.)
R ²⁷ to R ²⁹ in general formula (13) each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyloxy group having 2 to 20 carbon atoms. carbonyl group, aryloxycarbonyl group having 7 to 20 carbon atoms, cyano group, nitro group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, hydroxyl group, amino group, or 1 to 1 carbon atoms A hydrogen atom or an alkyl group having 1 to 20 carbon atoms is preferred because of its high heat resistance.

The alkyl group having 1 to 20 carbon atoms in R ²⁷ to R ²⁹ is, for example, a linear group such as methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, etc. or a branched alkyl group. Aryl groups having 6 to 20 carbon atoms include, for example, phenyl group, p-tolyl group, p-(n-hexyl)phenyl group, p-(n-octyl)phenyl group, p-(2-ethylhexyl)phenyl group and the like. is mentioned. The alkyloxycarbonyl group having 2 to 20 carbon atoms includes, for example, methyloxycarbonyl group, ethyloxycarbonyl group, n-propyloxycarbonyl group and the like. The aryloxycarbonyl group having 7 to 20 carbon atoms includes, for example, a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group and the like. The alkoxy group having 1 to 20 carbon atoms includes, for example, methoxy group, ethoxy group, n-propoxy group and the like. The aryloxy group having 6 to 20 carbon atoms includes, for example, a phenoxy group, 4-methylphenoxy and the like. The alkylamino group having 1 to 20 carbon atoms includes, for example, methylamino group, ethylamino group, n-propylamino group and the like. Among them, the substituent R ²⁷ is preferably a methyl group, an ethyl group, or an n-propyl group, and the substituents R ²⁸ and R ²⁹ are preferably hydrogen atoms because of high heat resistance.

X ³ in general formula (13) is 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, It represents 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.

The alkyloxycarbonyl group having 2 to 20 carbon atoms in the substituent X ³ is, for example, a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group and the like, and the aryloxycarbonyl group having 7 to 20 carbon atoms includes, for example, a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 2,4-dimethylphenoxycarbonyl group, a 4-ethylphenoxycarbonyl group, and the like. . The alkoxy group having 1 to 20 carbon atoms includes, for example, methoxy group, ethoxy group and the like. The aryloxy group having 6 to 20 carbon atoms includes, for example, a phenoxy group, 4-methylphenoxy and the like. The alkylamino group having 1 to 20 carbon atoms includes, for example, methylamino group, ethylamino group, n-propylamino group and the like. An alkyloxycarbonyl group having 2 to 20 carbon atoms is preferred for its high solubility and high heat resistance.

p represents an integer of 20 to 5,000, and is preferably 40 to 2,000 because it is suitable for obtaining an organic thin film transistor with higher carrier mobility. q represents an integer of 0 to 2, preferably 1; r represents an integer of 0 to 2, preferably 0 or 1; It is more preferably 0.

A bond consisting of a solid line and a dotted line indicates a single bond or a double bond, preferably a single bond for thermal stability.

The polysulfones used as the polymer binder in the present invention are not particularly limited as long as they have a polysulfone structure.

(Here, the substituents R ³⁰ to R ³³ 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 ³⁰ to R ³³ is, for example, 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- Linear or branched alkyl groups such as ethyldecyl group and 2-hexyldecyl group can be mentioned.

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

The acrylonitrile-styrene copolymer used as the polymer binder in the present invention is a copolymer of acrylonitrile and styrene in an arbitrary ratio, exhibits good electrical properties, and exhibits a greater change in threshold voltage when bias stress is applied. The weight ratio of acrylonitrile to styrene is preferably 10:90 to 50:50, more preferably 20:80 to 40:60, because the weight ratio of acrylonitrile to styrene is 10:80 to 40:60.

The methyl methacrylate-styrene copolymer used as the polymer binder in the present invention is a copolymer of methyl methacrylate and styrene in an arbitrary ratio, exhibits good electrical properties, and changes in threshold voltage when bias stress is applied. The molar ratio of methyl methacrylate to styrene is preferably from 1:99 to 90:10, more preferably from 1:99 to 70:30, because the reliability is improved such that the ratio becomes smaller.

The polymer used as the polymer binder in the present invention can be used after adjusting the surface energy with a surface treatment agent. A silane coupling agent can be used as the surface treatment agent, and specific examples thereof include 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, octyltrichlorosilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane and the like can be mentioned. As for the polymer used in the present invention, one type of polymer can be used alone, or two or more types of polymer can be used as a mixture. Furthermore, it is also possible to use a mixture of polymers with different molecular weights.

The coating method for forming an organic semiconductor layer using the solution for forming an organic semiconductor layer of the present invention is not particularly limited as long as it is a method capable of forming an organic semiconductor layer, and examples thereof include spin coating, drop casting, and dipping. simple coating methods such as coating and cast coating; printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing and offset printing; Spin coating, drop casting, and inkjet are preferable because they can be applied.

After applying the solution for forming an organic semiconductor layer of the present invention, the organic semiconductor layer can be formed using the solution for forming an organic semiconductor layer by removing the solvent by drying.

When removing the solvent from the applied organic semiconductor layer by drying, the drying conditions are not particularly limited. For example, the solvent can be removed by drying under normal pressure or under reduced pressure.

Although there is no particular limitation on the temperature for drying and removing the organic solvent from the coated organic semiconductor layer, the organic solvent can be efficiently removed by drying from the coated organic semiconductor layer, and the organic semiconductor layer can be formed. It is preferable to carry out in the temperature range of 10 to 150°C.

When removing the organic solvent from the applied organic semiconductor layer by drying, it is possible to control the crystal growth of the aromatic compound represented by the general formula (1) by adjusting the vaporization rate of the removed organic solvent. .

The film thickness of the organic semiconductor layer formed by the organic semiconductor layer forming solution of the present invention is not limited, and is preferably in the range of 1 nm to 1 μm, more preferably in the range of 10 nm to 300 nm, since good carrier transfer can be obtained. is more preferable.

Further, the obtained organic semiconductor layer may be annealed at 40 to 180° C. after forming the organic semiconductor layer.

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 containing the organic semiconductor layer, particularly as an organic thin film transistor containing the organic semiconductor layer.

An organic thin film transistor can be obtained by laminating an organic semiconductor layer having a source electrode and a drain electrode and a gate electrode on a substrate with an insulating layer interposed therebetween. By using an organic semiconductor layer formed from a solution, it is possible to obtain an organic thin film transistor exhibiting excellent semiconductor and electrical characteristics.

FIG. 1 shows a cross-sectional structure 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. 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, formed from the solution for forming an organic semiconductor layer of the present invention. The organic semiconductor layer can be applied to any organic thin film transistor.

The substrate according to the present invention is not particularly limited. Plastic substrates such as polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate; glass, quartz, aluminum oxide, silicon, high-doped silicon , silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. Note that when highly doped silicon is used for the substrate, the substrate can also serve as a gate electrode.

The gate electrode according to the present invention is not particularly limited. organic materials such as doped conductive polymers (eg PEDOT-PSS).

In addition, the inorganic materials described above can also be used as a metal nanoparticle ink without any problem. Polar solvents such as water, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol; carbon number such as hexane, heptane, octane, decane, dodecane, tetradecane, etc. 6-14 aliphatic hydrocarbon solvents; Aromatic hydrocarbon solvents having 7 to 14 carbon atoms such as 1,2-dimethylanisole, 2,3-dimethylanisole and 3,4-dimethylanisole are preferred. After applying the nanoparticle ink, it is preferable to perform an annealing treatment in a temperature range of 80° C. to 200° C. in order to improve conductivity.

The gate insulating layer according to the present invention is not particularly limited, and examples include silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide and titanium. Inorganic materials such as barium oxide and bismuth titanate; phthalate, polyethyl cinnamate, polymethyl cinnamate, polyethyl crotonate, polyethersulfone, polypropylene-co-1-butene, polyisobutylene, polypropylene, polycyclopentane, polycyclohexane, polycyclohexane-ethylene copolymer, Polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, BCB resin (trade name: Cycloten, Dow Chemical Co.), Cytop (trademark), Teflon (trademark), Parylene C, etc. and the polymer insulating material (polymer gate insulating layer) to which the coating method can be applied because the manufacturing method is simple.

The solvent used for dissolving the polymer material is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents having 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, and tetradecane; Ether solvents such as ethane and dioxane; Alcohol solvents such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 2-ethylhexanol, and tetrahydrofurfuryl alcohol; Acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, etc. Ketone solvents; ester solvents such as ethyl acetate, γ-butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate; amide solvents such as DMF and NMP; 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 Glycol solvents such as acetate, 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; perfluorohexane, perfluorooctane, 2-(pentafluoroethyl ) fluorinated solvents such as hexane and 3-(pentafluoroethyl)heptane.

The concentration of the polymeric insulating material is, for example, 0.1-10.0% by weight at a temperature of 20-40.degree. The film thickness of the insulating layer obtained at this concentration is not limited, and is preferably 100 nm to 1 μm, more preferably 150 nm to 900 nm, from the viewpoint of insulation resistance.

The surfaces of these gate insulating layers are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrimethoxysilane. Those modified with silanes such as chlorosilane and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid; and silylamines such as hexamethyldisilazane can also be used. In general, surface treatment of the gate insulating layer increases the crystal grain size of the organic semiconductor material and improves the molecular orientation, which is preferable for improving carrier mobility, improving the current on/off ratio, and lowering the threshold voltage. You get results.

The material of the source electrode and the drain electrode of the organic thin film transistor of the present invention is not particularly limited, and the same material as that of the gate electrode can be used. may be laminated. Moreover, in order to increase the efficiency of carrier injection, these electrode materials can be subjected to surface treatment. Examples of surface treatment agents used for surface treatment include benzenethiol, pentafluorobenzenethiol, 4-fluorobenzenethiol, and 4-methoxybenzenethiol.

The organic thin film transistor of the present invention preferably has a carrier mobility of 0.20 cm ² /V·sec or more for fast operability. Also, the current on/off ratio is preferably 1.0×10 ⁶ or more for high switching characteristics.

The organic thin film transistor of the present invention is used for organic semiconductor layer of transistors such as electronic paper, organic EL display, liquid crystal display, IC tag (RFID tag), pressure sensor, biosensor; organic EL display material; organic semiconductor laser material; organic thin film Solar cell material; It can be used for electronic materials such as photonic crystal materials, and since the aromatic compound represented by the general formula (1) forms a crystalline thin film, it can be used as a semiconductor layer for organic thin-film transistors. preferable.

The novel aromatic compounds of the present invention provide high carrier mobility while possessing high heat resistance and suitable solubility and HOMO levels. Therefore, it is possible to provide an organic thin film transistor exhibiting excellent semiconductor characteristics by coating, and the effect is extremely high.

; It is a figure which shows the structure by the cross-sectional shape of an organic thin-film transistor.

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

¹ H NMR spectrum, gas chromatography-mass spectrum (GCMS), and liquid chromatography-mass spectrum (LCMS) analysis were used for product identification.

< ¹ H NMR spectrum analysis>
Apparatus; JEOL, (trade name) Delta V5 (400 MHz)
Measurement temperature; 23°C (if no temperature is specified)
<Gas Chromatography-Mass Spectrum Analysis>
Apparatus; (trade name) Autosystem XL (MS part; Turbomass Gold) manufactured by Perkin Elmer (Synthesis Examples 1, 2, 4, 6)
Apparatus; manufactured by Shimadzu Corporation, (trade name) QP-2010 Ultra (Synthesis Examples 9 and 11)
Column; J&W Scientific, (trade name) DB-1, 30m.
MS ionization; electron impact (EI) method (70 electron volts)
<Direct introduction mass spectrum analysis>
Apparatus; manufactured by Shimadzu Corporation, (trade name) QP-2010 Ultra
MS ionization; electron impact (EI) method (70 electron volts)
<Liquid chromatography-mass spectrum (LCMS) analysis>
Apparatus; Bruker Daltonics, (trade name) microTOF focus
MS ionization; atmospheric pressure chemical ionization (APCI) method LC conditions; conditions described in the liquid chromatography analysis section below. ) analysis was used. Purity determination of biphenylene derivatives was also carried out using liquid chromatography analysis.

<Thin layer chromatography analysis>
PLC silica gel 60F254 0.5 mm for thin layer chromatography manufactured by Merck was used, and hexane and/or toluene was used as a developing solvent.

<Gas chromatography analysis>
Apparatus; manufactured by Shimadzu Corporation, (trade name) GC2014
Column; manufactured by J&W Scientific, (trade name) DB-1, 30m
<Liquid chromatography analysis>
Apparatus; manufactured by Tosoh (controller; PX-8020, pump; CCPM-II, degasser; SD-8022)
Column; manufactured by Tosoh, (trade name) ODS-100V, 5 μm, 4.6 mm × 250 mm
Column temperature; 33°C
Eluent; dichloromethane: acetonitrile = 2: 8 (volume ratio)
Flow rate: 1.0 ml/min Detector: UV (manufactured by Tosoh, (trade name) UV-8020, wavelength: 254 nm).

A DSC (differential scanning calorimeter) was used to measure the melting point of the biphenylene derivative.

<DSC measurement>
Apparatus; manufactured by SII Nanotechnology, model; DSC6220
Temperature increase/decrease rate; 10°C/min
Scanning range; -10°C to 300°C
Synthesis Example 1 (Synthesis of 2,2'-dibromo-4,5'-difluorobiphenyl) (Step A1)
Under a nitrogen atmosphere, 3.95 g (13.1 mmol) of 1-bromo-4-fluoro-2-iodobenzene (Tokyo Kasei Kogyo) and 15 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The solution was cooled to 0° C. and 6.8 ml (13.6 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0° C. for 15 minutes to prepare 1-bromo-4-fluorophenyl-2-magnesium chloride.

On the other hand, 2.42 g (17.7 mmol) of zinc chloride (Wako Pure Chemical Industries) and 19 ml of THF (dehydrated grade) were added to another 100 ml Schlenk reactor under a nitrogen atmosphere and cooled to 0°C. The 1-bromo-4-fluorophenyl-2-magnesium chloride solution previously prepared was added dropwise to the obtained white fine slurry solution using a Teflon (registered trademark) cannula, and 2 ml of THF (dehydrated grade) was added. A 100 ml Schlenk reaction vessel and a Teflon (registered trademark) cannula were charged with washing. The resulting mixture was stirred while gradually warming to room temperature. To the resulting slurry of 1-bromo-4-fluorophenyl-2-zinc chloride, 3.18 g (10.5 mmol) of 2-bromo-4-fluoro-1-iodobenzene (Tokyo Chemical Industry Co., Ltd.) and tetrakis ( Triphenylphosphine)palladium (Tokyo Chemical Industry Co., Ltd.) 115 mg (0.0995 mmol, 0.948 mol % relative to 2-bromo-4-fluoro-1-iodobenzene) was added. After carrying out the reaction at 50° C. for 7 hours, the reaction was stopped by cooling the vessel with water and adding 1 M hydrochloric acid. Toluene and brine were added, the organic phase was separated, the organic phase was washed with brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the obtained residue was purified by silica gel column chromatography (solvent: hexane). 3.48 g of colorless oil of 2,2'-dibromo-4,5'-difluorobiphenyl were obtained (yield 94%).

MS m/z: 350 (M ⁺ +2, 51%), 348 (M ⁺ , 100%), 346 (M ⁺ -2, 53).

¹ H NMR (CDCl ₃ ): δ=7.62 (dd, J=8.7 Hz, 5.4 Hz, 1 H), 7.43 (dd, J=8.2 Hz, 2.3 Hz, 1 H),7. 27-7.19 (m, 1H), 7.11 (dt, J=8.2Hz, 2.7Hz, 1H), 7.04-6.96 (m, 2H).

Synthesis Example 2 (Synthesis of 2,6-difluorobiphenylene) (Step B1)
In a nitrogen atmosphere, 3.30 g (9.48 mmol) of 2,2′-dibromo-4,5′-difluorobiphenyl synthesized in Synthesis Example 1 and 160 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reactor. This mixture was cooled to −78° C., and 12.5 ml (20.0 mmol) of hexane solution of n-butyllithium (Kanto Kagaku, 1.6 M) was added dropwise. The mixture was aged at -78°C for 1 hour. 3.75 g (27.9 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was introduced into the flask at -78°C. The resulting mixture was stirred while gradually warming to room temperature. After adding 1M hydrochloric acid to the reaction mixture, toluene was added to separate the phases. The organic phase was washed twice with brine and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). 1.48 g of a pale yellow solid of 2,6-difluorobiphenylene was obtained (91% yield).

MS m/z: 188 (M ⁺ , 100%).

¹ H NMR (CDCl ₃ ): δ=6.56 (dd, J=11 Hz, 4.0 Hz, 2H), 6.42-6.35 (m, 4H).

Synthesis Example 3 (Synthesis of 2,6-difluoro-1,5-diiodobiphenylene) (Step C1)
Under a nitrogen atmosphere, 516 mg (5.10 mmol) of diisopropylamine and 9 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. This mixture was cooled to −40° C., and 3.1 ml (5.0 mmol) of hexane solution of n-butyllithium (Kanto Kagaku, 1.6 M) was added dropwise to prepare LDA. This mixture was cooled to −78° C., 380 mg (2.02 mmol) of 2,6-difluorobiphenylene synthesized in Synthesis Example 2 was gradually added thereto, and the mixture was stirred at −78° C. to −60° C. for 2.5 hours. did. The resulting mixture was brought to −78° C. and a solution consisting of 1.26 g (4.96 mmol) of iodine and 4 ml of THF (dehydrated grade) was added dropwise. The resulting mixture was stirred while gradually warming to room temperature. After cooling the reaction mixture to 0° C., water and toluene were added and the phases were separated. The aqueous phase was extracted with toluene, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 471 mg of 2,6-difluoro-1,5-diiodobiphenylene as a pale yellow solid (yield 53%).

¹ H NMR (CDCl ₃ ): δ = 6.68 (dd, J = 7.3 Hz, 3.6 Hz, 2H), 6.44 (dd, J = 9.6 Hz, 7.3 Hz, 2H).

Synthesis Example 4 (Synthesis of 2,6-difluoro-1,5-dioctinylbiphenylene) (Step D1)
Under a nitrogen atmosphere, 453 mg (1.02 mmol) of 2,6-difluoro-1,5-diiodobiphenylene synthesized in Synthesis Example 3 and 64 dichlorobis(triphenylphosphine)palladium (Wako Pure Chemical Industries) were placed in a 100 ml Schlenk reaction vessel. 3 mg (0.0916 mol), copper (I) iodide (Wako Pure Chemical Industries) 35.9 mg (0.188 mmol), toluene 9 ml, and triethylamine 9 ml were added. Further, 337 mg (3.06 mmol) of 1-octyne (Wako Pure Chemical Industries) was added. The mixture was reacted at 30° C. for 10 hours. Toluene and water were added to the resulting reaction mixture, and after phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). 293 mg of a yellow solid of 2,6-difluoro-1,5-dioctinylbiphenylene was obtained (yield 71%).

MS m/z: 406 (M ⁺ +2, 6.0%), 405 (M ^{+ +1} , 34%), 404 (M ⁺ , 100%).

¹ H NMR (CDCl ₃ ): δ = 6.54 (dd, J = 7.3 Hz, 4.1 Hz, 2H), 6.40 (dd, J = 11 Hz, 7.7 Hz, 2H), 2.44 ( t, J = 7.7Hz, 4H), 1.61 (m, 4H), 1.46 (m, 4H), 1.32 (m, 8H), 0.89 (t, J = 7.7Hz, 6H).

Example 1 Synthesis of (aromatic compound (1-1a, R ⁹ =C ₆ H ₁₃ )) (step E1)
Under a nitrogen atmosphere, 287 mg (0.709 mmol) of 2,6-difluoro-1,5-dioctinylbiphenylene synthesized in Synthesis Example 4 and sodium sulfide nonahydrate (Wako Pure Chemical Industries) were placed in a 100 ml Schlenk reaction vessel. 613 mg (2.55 mmol) and 6 ml of DMSO (Wako Pure Chemical Industries) were added. The mixture was heated to 80° C. and stirred for 5 hours. After cooling the resulting reaction mixture to 0° C., water and toluene were added. After phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). Further, recrystallization from hexane was performed twice to obtain 184 mg of yellow solid of 2,7-dihexyldithienobiphenylene (1-1a, compound 1) (yield 61%). Purity was 99.3% by LC analysis.

Melting point: 155°C
MS m/z: 434 (M ⁺ +2, 14%), 433 (M ^{+ +1} , 34%), 432 (M ⁺ , 100%), 361 (M ⁺ -C ₅ H ₁₁ , 90%), 290 ( M ⁺ -2C ₅ H ₁₁ , 55%).

¹ H NMR (CDCl ₃ ): δ = 7.04 (d, J = 7.3 Hz, 2H), 6.60 (s, 2H), 6.54 (d, J = 7.3 Hz, 2H), 2 .78 (t, J = 7.2 Hz, 4H), 1.70 (m, 4H), 1.39 (m, 4H), 1.32 (m, 8H), 0.90 (t, J = 6 .8Hz, 6H).

The HOMO level was -5.31 eV from the CV measurement.

Synthesis Example 5 (Synthesis of 2,6-dibromo-3,7-difluorobiphenylene) (Step C4)
In a nitrogen atmosphere, 351 mg (1.86 mmol) of 2,6-difluorobiphenylene synthesized in Synthesis Example 2 and 7 ml of DMF (dehydrated grade) were added to a 100 ml Schlenk reactor. Here, 954 mg (5.36 mmol) of NBS (Wako Pure Chemical Industries) was added at room temperature. After stirring at 40° C. for 10 hours, the resulting reaction mixture was cooled to room temperature. Water and toluene were added and the phases separated. The organic phase was washed twice with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was recrystallized from a mixed solvent of hexane:toluene=1:2 to obtain 302 mg of yellow needle crystals of 2,6-dibromo-3,7-difluorobiphenylene (yield 47%).

¹ H NMR (CDCl ₃ ): δ = 6.82 (d, J = 5.9 Hz, 2H), 6.49 (d, J = 6.4 Hz, 2H).

Synthesis Example 6 (Synthesis of 2,6-difluoro-3,7-dioctinylbiphenylene) (Step D4)
Under a nitrogen atmosphere, 270 mg (0.780 mmol) of 2,6-dibromo-3,7-difluorobiphenylene synthesized in Synthesis Example 5 and 45.0 mg (0.780 mmol) of 2,6-dibromo-3,7-difluorobiphenylene synthesized in Synthesis Example 5 and dichlorobis(triphenylphosphine)palladium (Wako Pure Chemical Industries) were placed in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere. 3 mg (0.0645 mol), copper (I) iodide (Wako Pure Chemical Industries) 26.0 mg (0.136 mmol), toluene 3 ml, and triethylamine 5 ml were added. Further, 560 mg (5.08 mmol) of 1-octyne (Wako Pure Chemical Industries) was added. The mixture was reacted at 60° C. for 35 hours. The resulting reaction mixture was cooled to room temperature and toluene and water were added. After phase separation, the organic phase was washed twice with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). 303 mg of a yellow solid of 2,6-difluoro-3,7-dioctinylbiphenylene was obtained (yield 96%).

MS m/z: 406 (M ⁺ +2, 5.0%), 405 (M ^{+ +1} , 36%), 404 (M ⁺ , 100%).

¹ H NMR (CDCl ₃ ): δ = 6.60 (d, J = 6.0 Hz, 2H), 6.42 (d, J = 7.3 Hz, 2H), 2.42 (t, J = 6.0 Hz). 9Hz, 4H), 1.59 (m, 4H), 1.44 (m, 4H), 1.32 (m, 8H), 0.90 (t, J = 6.8Hz, 6H).

Example 2 Synthesis of (aromatic compound (1-3a, R ⁹ =C ₆ H ₁₃ )) (step E4)
Under a nitrogen atmosphere, 107 mg (0.264 mmol) of 2,6-difluoro-3,7-dioctinylbiphenylene synthesized in Synthesis Example 6 and sodium sulfide nonahydrate (Wako Pure Chemical Industries) were placed in a 100 ml Schlenk reaction vessel. 252 mg (1.05 mmol) and 3 ml of DMSO (Wako Pure Chemical Industries) were added. The mixture was heated to 80° C. and stirred for 5 hours. After cooling the resulting reaction mixture to 0° C., water and toluene were added. After phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane/toluene=1/1 to 0:1). Further, recrystallization from toluene was performed twice to obtain 72 mg of yellow solid of 2,7-dihexyldithienobiphenylene (1-3a, compound 2) (yield 62%). Purity was 99.2% by LC analysis.

Melting point: >300°C
MS m/z: 434 (M ⁺ +2, 13%), 433 (M ^{+ +1} , 36%), 432 (M ⁺ , 100%), 361 (M ⁺ -C ₅ H ₁₁ , 88%), 290 ( M ⁺ -2C ₅ H ₁₁ , 52%).

¹ H NMR (CDCl ₃ ): δ = 7.04 (s, 2H), 6.95 (s, 2H), 6.79 (s, 2H), 2.81 (t, J = 7.2 Hz, 4H ), 1.70 (m, 4H), 1.38 (m, 4H), 1.32 (m, 8H), 0.89 (t, J = 6.8 Hz, 6H).

The HOMO level was -5.40 eV from the CV measurement.

Synthesis Example 7 (Synthesis of 2,6-difluoro-1,5-didecynylbiphenylene) (Step D1)
In Synthesis Example 4, the same procedure as in Synthesis Example 4 was repeated except that 1-decyne (Wako Pure Chemical Industries, Ltd.) was used instead of 1-octyne to obtain a yellow color of 2,6-difluoro-1,5-didecynylbiphenylene. A solid was obtained (71% yield).

¹ H NMR (CDCl ₃ ): δ = 6.53 (dd, J = 7.3 Hz, 4.1 Hz, 2H), 6.39 (dd, J = 11 Hz, 7.7 Hz, 2H), 2.43 ( t, J = 7.7Hz, 4H), 1.60 (m, 4H), 1.46 (m, 4H), 1.32 (m, 16H), 0.89 (t, J = 7.7Hz, 6H).

Example 3 Synthesis of (aromatic compound (1-1a, R ⁹ =C ₈ H ₁₇ )) (Step E1)
Example 1 except that 2,6-difluoro-1,5-didecynylbiphenylene synthesized in Synthesis Example 7 was used instead of 2,6-difluoro-1,5-dioctinylbiphenylene. 2,7-dioctyldithienobiphenylene (1-1a, compound 3) as a yellow solid was obtained by repeating the same operation (yield 61%). Purity was 99.3% by LC analysis.

Melting point: 140°C
MS (APCI ⁺ ) m/z: 489 (M ⁺ +H).

¹ H NMR (CDCl ₃ ): δ = 7.03 (d, J = 7.3 Hz, 2H), 6.60 (s, 2H), 6.54 (d, J = 7.3 Hz, 2H), 2 .77 (t, J = 7.2Hz, 4H), 1.68 (m, 4H), 1.40-1.20 (m, 20H), 0.87 (t, J = 6.8Hz, 6H) .

The HOMO level was -5.29 eV from the CV measurement.

Synthesis Example 8 (Synthesis of 2,6-difluoro-1,5-didodecynylbiphenylene) (Step D1)
In Synthesis Example 4, the same procedure as in Synthesis Example 4 was repeated except that 1-dodecine (Wako Pure Chemical Industries) was used instead of 1-octyne to obtain 2,6-difluoro-1,5-didodecynylbiphenylene. A yellow solid was obtained (78% yield).

¹ H NMR (CDCl ₃ ): δ = 6.52 (dd, J = 7.3 Hz, 4.1 Hz, 2H), 6.38 (dd, J = 11 Hz, 7.7 Hz, 2H), 2.42 ( t, J = 7.7Hz, 4H), 1.59 (m, 4H), 1.46 (m, 4H), 1.32 (m, 24H), 0.88 (t, J = 7.7Hz, 6H).

Example 4 Synthesis of (aromatic compound (1-1a, R ⁹ =C ₁₀ H ₂₁ )) (step E1)
Example 1, except that 2,6-difluoro-1,5-didodecynylbiphenylene synthesized in Synthesis Example 8 was used instead of 2,6-difluoro-1,5-dioctynylbiphenylene. The same operation as in 1 was repeated to obtain a yellow solid of 2,7-didecyldithienobiphenylene (1-1a, compound 4) (yield 61%). Purity was 99.3% by LC analysis.

Melting point: 132°C
MS (APCI ⁺ ) m/z: 545 (M ⁺ +H).

¹ H NMR (CDCl ₃ ): δ = 7.02 (d, J = 7.3 Hz, 2H), 6.59 (s, 2H), 6.53 (d, J = 7.3 Hz, 2H), 2 .76 (t, J = 7.2Hz, 4H), 1.68 (m, 4H), 1.40-1.20 (m, 28H), 0.87 (t, J = 6.8Hz, 6H) .

The HOMO level was -5.27 eV from the CV measurement.

Synthesis Example 9 (Synthesis of 2-bromo-1-fluoro-3-iodobenzene)
Under a nitrogen atmosphere, 5.76 g (56.9 mmol) of diisopropylamine and 115.0 ml of THF (dehydrated grade) were added to a 500 ml Schlenk reaction vessel. This solution was cooled to −50° C., and 34.0 ml (54.4 mmol) of hexane solution of n-butyllithium (1.6M, Tokyo Chemical Industry Co., Ltd.) was added dropwise to prepare LDA. The mixture was cooled to −78° C., 11.5 g (51.8 mmol) of 1-fluoro-3-iodobenzene (Tokyo Kasei Kogyo Co., Ltd.) was added, and the mixture was kept at −78° C. for 2 hours. A solution prepared by dissolving 34.4 g (103.6 mmol) of tetrabromomethane (Tokyo Chemical Industry Co., Ltd.) in 160.0 ml of THF (dehydrated grade) was added dropwise thereto at −78° C., and the temperature was gradually raised to room temperature. Water and toluene were added to the resulting reaction mixture and the phases were separated. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane). 3.0 g of methanol (Wako Pure Chemical Industries, Ltd.) was added, and the mixture was recrystallized by raising the temperature to 50° C. to obtain 7.43 g of a white solid of 2-bromo-1-fluoro-3-iodobenzene (yield: 43 .3%).

MS m/z: 302 (M ⁺ +2, 75%), 300 (M ⁺ , 78%), 175 (M ⁺ +2-I, 38%), 173 (M ⁺ -I, 39%), 94 (M ⁺ -BrI, 100%).

¹ H NMR (CDCl ₃ ): δ=7.68-7.64 (m, 1H), 7.12-7.08 (m, 1H), 7.05-7.00 (m, 1H)
Synthesis Example 10 (Synthesis of 2,2'-dibromo-3,6'-difluorobiphenyl) (Step A2)
Under a nitrogen atmosphere, 4.89 g (16.3 mmol) of 1-bromo-3-fluoro-2-iodobenzene (Tokyo Kasei Kogyo) and 50.0 ml of THF (dehydrated grade) were added to a 200 ml Schlenk reactor. The solution was cooled to 0° C. and 8.4 ml (19.8 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0° C. for 20 minutes to prepare 1-bromo-3-fluorophenyl-2-magnesium chloride.

On the other hand, 3.28 g (24.1 mmol) of zinc chloride (Wako Pure Chemical Industries) and 30 ml of THF (dehydrated grade) were added to another 300 ml Schlenk reactor under a nitrogen atmosphere and cooled to 0°C. Into this obtained white fine slurry solution, the previously prepared 1-bromo-3-fluorophenyl-2-magnesium chloride solution was added dropwise using a Teflon (registered trademark) cannula, and 2 ml of THF (dehydrated grade) was added. A 100 ml Schlenk reaction vessel and a Teflon (registered trademark) cannula were charged with washing. The resulting mixture was stirred while gradually warming to room temperature. To the resulting slurry of 1-bromo-3-fluorophenyl-2-zinc chloride was added 3.51 g (11.7 mmol) of 2-bromo-1-fluoro-3-iodobenzene synthesized in Synthesis Example 9 and tetrakis as a catalyst. 1.40 g (1.2 mmol, 10 mol % of 2-bromo-1-fluoro-3-iodobenzene) of (triphenylphosphine) palladium (Tokyo Chemical Industry) was added. After carrying out the reaction at 60° C. for 3 hours, the reaction was terminated by cooling the vessel with water and adding 1 M hydrochloric acid. Toluene was added, the organic phase was separated and the organic phase was dried over anhydrous sodium sulfate. After concentration under reduced pressure, the obtained residue was purified by silica gel column chromatography (solvent: hexane). 2.90 g of a colorless solid of 2,2'-dibromo-3,6'-difluorobiphenyl was obtained (yield 71.3%).

¹ H NMR (CDCl ₃ ): δ=7.50 (d, J=8.2 Hz, 1H), 7.42-7.36 (m, 1H), 7.33-7.26 (m, 1H) , 7.23-7.18 (m, 1H), 7.17-7.12 (m, 1H), 7.05-6.96 (d, J=7.3 Hz 1H).

Synthesis Example 11 (Synthesis of 1,5-difluorobiphenylene) (Step B3)
In a nitrogen atmosphere, 395.5 mg (1.1 mmol) of 2,2′-dibromo-3,6′-difluorobiphenyl synthesized in Synthesis Example 10 and 20 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reactor. The mixture was cooled to −78° C., and 2.9 ml (4.6 mmol) of hexane solution of n-butyllithium (Kanto Kagaku, 1.6 M) was added dropwise. This mixture was aged at -78°C for 1 hour, then heated to -40°C over 10 minutes and aged for 1 hour. 1.50 g (4.8 mmol) of N-fluorobenzenesulfonimide (Tokyo Kasei Kogyo Co., Ltd.) was added to this. The resulting mixture was stirred while gradually warming to room temperature. After adding 1M hydrochloric acid to the reaction mixture, toluene was added to separate the phases. The organic phase was dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). 130.0 mg of pale yellow solid of 1,5-difluorobiphenylene was obtained (yield 51.7%).

MS m/z: 188 (M ⁺ , 100%), 168 (M ⁺ -HF, 15%) 94 (M ⁺ -C ₆ H ₃ F, 15%).

¹ H NMR (CDCl ₃ ): δ=6.80 (ddd, 2H) δ=6.56-6.50 (m, 4H).

Synthesis Example 12 (Synthesis of biphenylene-1,5-bis(thioacetaldehyde dimethylacetal) (step C3)
Under a nitrogen atmosphere, 57.6 mg (0.31 mmol) of 1,5-difluorobiphenylene synthesized in Synthesis Example 11 and 398.0 mg (1. 65 mmol) and 4 ml of NMP (Wako Pure Chemical Industries) were added. The mixture was stirred at 110° C. for 6 hours. 578.2 mg (3.42 mmol) of 2-bromoacetaldehyde dimethylacetal (Tokyo Chemical Industry Co., Ltd.) was added to the obtained reaction mixture, and the mixture was heated and stirred at 100° C. for 3 hours. After cooling the resulting reaction mixture to room temperature, water and toluene were added. After phase separation, the organic phase was dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane/ethyl acetate=10/1-10/2). Further, low-boiling components were removed under reduced pressure to obtain 65.4 mg of a yellow solid of biphenylene-1,5-bis(thioacetaldehyde dimethylacetal) (yield 64.7%).

¹ H NMR (CDCl ₃ ): δ = 6.70 (d, J = 5.5 Hz, 2H), 6.69 (d, J = 1.4 Hz, 2H), 6.54 (dd, J = 5.5 Hz). 5 Hz, 1.4 Hz, 2 H), 4.53 (t, J=5.9 Hz, 2 H), 3.38 (s, 12 H), 3.10 (d, J=5.9, Hz, 4 H).

Example 5 (Synthesis of dithienobiphenylene derivative (D3 step)
Under a nitrogen atmosphere, 57.7 mg (0.15 mmol) of biphenylene-1,5-bis(thioacetaldehyde dimethylacetal) synthesized in Synthesis Example 12, 109.4 mg of polyphosphoric acid (Wako Pure Chemical Industries) were placed in a 50 ml Schlenk reaction vessel. and 4 ml of chlorobenzene (Wako Pure Chemical Industries) were added. The mixture was stirred at 130° C. for 5 hours. After cooling the resulting reaction mixture to room temperature, water and toluene were added. After phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent; hexane/ethyl acetate = 10/1 to 10/2) to obtain 22.5 mg of a yellow solid of dithienobiphenylene derivative ( 55% yield).

MS m/z: 264 (M ⁺ ).

Example 6 Synthesis of (aromatic compound (1-2a, R ⁹ =C ₈ H ₁₇ )) (Step E3)
Under a nitrogen atmosphere, 22.5 mg (0.085 mmol) of the dithienobiphenylene derivative synthesized in Example 5 and 4 ml of THF (dehydrated grade) were added to a 50 ml Schlenk reactor. The mixture was cooled to 0° C., and 0.20 ml (0.32 mmol) of a hexane solution of n-butyllithium (1.6M, Tokyo Chemical Industry Co., Ltd.) was added dropwise. After aging this mixture at 60° C. for 2 hours, 136 mg (0.567 mmol) of 1-iodooctane (Wako Pure Chemical Industries) was added. The resulting mixture was stirred at 60° C. for 7 hours. The reaction mixture was ice-cooled, 1M hydrochloric acid 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 resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 17 mg of a yellow solid of 2,7-dioctyldithienobiphenylene ((1-2a), compound 5) (yield 41%). .

MS (APCI ⁺ ) m/z: 489 (M ⁺ +H).

The HOMO level was -5.30 eV from the CV measurement.

Synthesis Example 13 (Synthesis of 1,5-bis(3-chloro-2-thienyl)-2,6-difluorobiphenylene) (Step D5)
Under a nitrogen atmosphere, 4.96 g (41.9 mmol) of 3-chlorothiophene, 23 ml of chloroform, and 23 ml of acetic acid were added to a 100 ml Schlenk reactor. 8.16 g (45.8 mmol) of NBS (Wako Pure Chemical Industries) was put into this. After stirring at room temperature for 8 hours, the resulting reaction mixture was ice-cooled and quenched by adding 30 ml of saturated sodium bicarbonate water. It was extracted twice with dichloromethane, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was dried under reduced pressure of 1700 Pa using a diaphragm pump to obtain 7.94 g of pale red oil of 2-bromo-3-chlorothiophene (yield 96%).

¹ H NMR (CDCl ₃ ): δ = 6.82 (d, J = 5.9 Hz, 2H), 6.49 (d, J = 6.4 Hz, 2H).

Under a nitrogen atmosphere, 71.2 mg (0.361 mmol) of 2-bromo-3-chlorothiophene synthesized above and 3 ml of THF (dehydrated grade) were added to a 50 ml Schlenk reaction vessel. The solution was cooled to 0° C. and 0.20 ml (0.40 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0° C. for 10 minutes to prepare 3-chloro-2-thienyl-2-magnesium chloride.

Meanwhile, 87.8 mg (0.644 mmol) of zinc chloride (Wako Pure Chemical Industries) and 2 ml of THF (dehydrated grade) were added to a 50 ml Schlenk reactor under a nitrogen atmosphere, and cooled to 0°C. Into this obtained white fine slurry solution, the previously prepared 3-chloro-2-thienyl-2-magnesium chloride solution was added dropwise using a Teflon (registered trademark) cannula, and further THF (dehydration grade) 1 ml was added. A 50 ml Schlenk reaction vessel and a Teflon (registered trademark) cannula were charged while washing. The resulting mixture was stirred while gradually warming to room temperature. To the resulting slurry of 3-chloro-2-thienyl-2-zinc chloride was added 49.3 mg (0.112 mmol) of 2,6-difluoro-1,5-diiodobiphenylene synthesized in Synthesis Example 3 and tetrakis as a catalyst. 3.4 mg (0.00294 mmol, 2.63 mol % relative to 2,6-difluoro-1,5-diiodobiphenylene) of (triphenylphosphine) palladium (Tokyo Chemical Industry Co., Ltd.) was added. After carrying out the reaction at 60° C. for 7 hours, the reaction was stopped by cooling the vessel with water and adding 1M hydrochloric acid. Toluene and brine were added, the organic phase was separated, the organic phase was washed with water and brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was purified by silica gel column chromatography (solvent; hexane/toluene=1/0 to 95/5). 15.1 mg of yellow solid of 1,5-bis(3-chloro-2-thienyl)-2,6-difluorobiphenylene was obtained (32% yield).

¹ H NMR (CDCl ₃ ): δ = 7.42 (d, J = 5.2 Hz, 2H), 7.04 (d, J = 5.2 Hz, 2H), 6.55-6.51 (m, 4H).

Example 7 Synthesis of (Bis(dithieno)biphenylene derivative) (Step E5)
Under a nitrogen atmosphere, 15.1 mg (0.0358 mmol) of 1,5-bis(3-chloro-2-thienyl)-2,6-difluorobiphenylene synthesized in Synthesis Example 13, sodium sulfide 9 44.2 mg (0.184 mmol) of hydrate (Wako Pure Chemical Industries) and 2 ml of NMP (Wako Pure Chemical Industries) were added. The mixture was heated to 170° C. and stirred for 4 hours. After cooling the resulting reaction mixture to 0° C., water and toluene were added. After phase separation, the organic phase was washed with water, brine and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane/toluene = 1/1) to obtain 7.6 mg of a yellow solid of bis(dithieno)biphenylene derivative (yield: 56 .7%).

¹ H NMR (CDCl ₃ ): δ=7.55 (d, J=4.8 Hz, 2H), 7.01 (d, J=6.8 Hz, 2H), 6.82 (d, J=8. 0 Hz, 2H), 6.58 (d, J = 6.8 Hz, 2H).

Example 8 Synthesis of (aromatic compound (1-11a, R ⁹ =C ₈ H ₁₇ )) (step F5)
In a nitrogen atmosphere, 7.3 mg (0.0194 mmol) of the bis(dithieno)biphenylene derivative synthesized in Synthesis Example 14 and 3 ml of THF (dehydrated grade) were added to a 50 ml Schlenk reactor. The mixture was cooled to 0° C., and 0.05 ml (0.08 mmol) of a hexane solution of n-butyllithium (1.6 M, Tokyo Chemical Industry Co., Ltd.) was added dropwise. After aging this mixture at 60° C. for 2 hours, 57.7 mg (0.240 mmol) of 1-iodooctane (Wako Pure Chemical Industries) was added. The resulting mixture was stirred at 60° C. for 8 hours. The reaction mixture was ice-cooled, a saturated aqueous solution of sodium hydrogencarbonate was added, and then toluene was added to separate the phases. The organic phase was washed with water and saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane) to obtain 7.0 mg of 2,8-dioctylbis(dithieno)biphenylene ((1-11a), compound 6) as a red solid (yield: rate 60.1%).

¹ H NMR (CDCl ₃ ): δ = 7.16 (d, J = 8.0 Hz, 2H), 6.91 (s, 2H), 6.74 (d, J = 8.0 Hz, 2H), 2 .92 (t, J = 7.6 Hz, 4H), 1.74 (m, J = 7.2 Hz, J = 8.4 Hz, 4H), 1.41 to 1.27 (m, 20H), 0.92. 88 (t, J = 6.8 Hz, 6H).

The HOMO level was -5.12 eV from the CV measurement.

Synthesis Example 14 (Synthesis of 1-bromo-5-hexyl-2-iodobenzene)
Under a nitrogen atmosphere, 444 mg (5.78 mmol) of ammonium acetate, 170 ml of acetonitrile, and 10.6 g (59.7 mmol) of 4-hexylaniline (Tokyo Kasei Kogyo Co., Ltd.) were added to a 300 ml single-neck eggplant flask reaction vessel. After cooling with ice, 11.2 g (62.7 mmol) of NBS (Wako Pure Chemical Industries) was added and stirred at room temperature for 7 hours. The resulting reaction mixture was concentrated on a rotary evaporator to remove low boilers. Toluene and water were added and after 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: hexane/toluene = 10/1 to 2/1) to obtain 11.9 g of red oil of 2-bromo-4-hexylaniline (yield 78% ).

11.7 g (45.8 mmol) of 2-bromo-4-hexylaniline obtained above and 210 ml of water were added to a 1-liter single-neck eggplant flask. This mixture was ice-cooled, 23.2 g of sulfuric acid (Wako Pure Chemical Industries) was added, and the mixture was stirred for 10 minutes. This mixture was cooled to 5° C., an aqueous solution of 4.17 g (60.4 mmol) of sodium nitrite (Wako Pure Chemical Industries) and 140 ml of water was added, and the mixture was stirred at 5 to 10° C. for 3 hours. An aqueous solution consisting of 61.8 g (372 mmol) of potassium iodide (Wako Pure Chemical Industries, Ltd.) and 140 ml of water was added thereto at 5° C. and stirred at room temperature for 2 hours. Further, the resulting mixture was stirred for 20 minutes while heating under reflux, cooled to room temperature, and an aqueous solution of 4.17 g (60.4 mmol) of sodium sulfite and 210 ml of water was added. The resulting reaction mixture was extracted with toluene, 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: hexane) to obtain 9.16 g of pale red oil of 1-bromo-5-hexyl-2-iodobenzene (yield 54%).

¹ H NMR (CDCl ₃ ): δ=7.72 (d, J=7.8 Hz, 1 H), 7.45 (d, J=1.8 Hz, 1 H), 6.81 (dd, J=8. 0Hz, J = 1.8Hz, 1H), 2.52 (t, J = 7.8Hz, 2H), 1.55 (m, 2H), 1.31 (m, 6H), 0.89 (t, J=7.3Hz, 3H).

Synthesis Example 15 (Synthesis of 2,2'-dibromo-4-hexyl-4'-fluorobiphenyl) (Step A7)
In a nitrogen atmosphere, 1.25 g (3.40 mmol) of 1-bromo-5-hexyl-2-iodobenzene synthesized in Synthesis Example 14 and 7 ml of THF (dehydrated grade) were added to a 50 ml Schlenk reactor. The solution was cooled to 0° C. and 1.8 ml (3.6 mmol) of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) in THF was added dropwise. The mixture was aged at 0° C. for 20 minutes to prepare 1-bromo-5-hexylphenyl-2-magnesium chloride.

Meanwhile, 668 mg (4.90 mmol) of zinc chloride (Wako Pure Chemical Industries) and 11 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reactor under a nitrogen atmosphere, and cooled to 0°C. Into this resulting fine white slurry solution, the previously prepared 1-bromo-5-hexylphenyl-2-magnesium chloride solution was added dropwise using a Teflon (registered trademark) cannula, and 2 ml of THF (dehydrated grade) was added. A 100 ml Schlenk reaction vessel and a Teflon (registered trademark) cannula were charged with washing. The resulting mixture was stirred while gradually warming to room temperature. To the resulting slurry of 1-bromo-5-hexylphenyl-2-zinc chloride, 1.19 g (3.96 mmol) of 2-bromo-4-fluoro-1-iodobenzene (Tokyo Chemical Industry Co., Ltd.) and tetrakis ( Triphenylphosphine)palladium (Tokyo Kasei Kogyo) 28.4 mg (0.0245 mmol, 0.618 mol % relative to 2-bromo-4-fluoro-1-iodobenzene) was added. After carrying out the reaction at 50° C. for 7 hours, the reaction was terminated by cooling the vessel with water and adding 1 M hydrochloric acid. Toluene and brine were added, the organic phase was separated, the organic phase was washed with brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the obtained residue was purified by silica gel column chromatography (solvent: hexane). 1.18 g of colorless oil of 2,2'-dibromo-4-hexyl-4'-fluorobiphenyl was obtained (yield 72%).

¹ H NMR (CDCl ₃ ): δ = 7.48 (d, J = 1.4 Hz, 1 H), 7.40 (dd, J = 8.2 Hz, 2.4 Hz, 1 H), 7.22 (dd, J = 8.7Hz, 6.0Hz, 1H), 7.18 (dd, J = 7.8Hz, 1.6Hz, 1H), 7.13 (s, 1H), 7.07 (dd, J = 8 .5Hz, 2.4Hz, 1H), 2.63 (t, J = 7.9Hz, 2H), 1.63 (m, 2H), 1.33 (m, 6H), 0.90 (t, J = 6.9Hz, 3H).

Synthesis Example 16 (Synthesis of 2-fluoro-7-hexylbiphenylene) (Step B7)
Under a nitrogen atmosphere, 1.18 g (2.85 mmol) of 2,2′-dibromo-4-hexyl-4′-fluorobiphenyl synthesized in Synthesis Example 15 and 70 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reactor. . The mixture was cooled to −78° C., and 4.7 ml (7.5 mmol) of hexane solution of n-butyllithium (1.6M, Tokyo Kasei Kogyo Co., Ltd.) was added dropwise. The mixture was aged at -78°C to -70°C for 1 hour. 1.46 g (10.8 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was introduced into the flask at -78°C. The resulting mixture was stirred while gradually warming to room temperature. After adding 1M hydrochloric acid to the reaction mixture, toluene was added to separate the phases. The organic phase was washed twice with brine and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). 485 mg of a pale yellow solid of 2-fluoro-7-hexylbiphenylene was obtained (67% yield).

¹ H NMR (CDCl ₃ ): δ=6.56 (d, J=6.9 Hz, 1H), 6.52 (s, 1H), 6.50-6.45 (m, 2H), 6.40 (dd, J = 7.3Hz, 2.2Hz, 1H), 6.34 (m, 1H), 2.40 (t, J = 7.8Hz, 2H), 1.52 (m, 2H), 1 .31 (m, 6H), 0.89 (t, J=7.1 Hz, 3H).

Synthesis Example 17 (Synthesis of 2,7-dibromo-3-fluoro-6-hexylbiphenylene) (Step C7)
In a nitrogen atmosphere, 481 mg (1.89 mmol) of 2-fluoro-7-hexylbiphenylene synthesized in Synthesis Example 16 and 12 ml of DMF (dehydrated grade) were added to a 200 ml single-neck eggplant flask reaction vessel. Here, 1.29 g (7.24 mmol) of NBS (Wako Pure Chemical Industries) was added at room temperature. After stirring at room temperature for 2 days and at 40° C. for 6 hours, the resulting reaction mixture was ice-cooled. Water and toluene were added and the phases separated. The organic phase was washed twice with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 284 mg of 2,7-dibromo-3-fluoro-6-hexylbiphenylene as a yellow solid (36% yield).

¹ H NMR (CDCl ₃ ): δ = 6.78 (s, 1H), 6.74 (d, J = 5.8 Hz, 1H), 6.57 (s, 1H), 6.50 (d, J = 6.9Hz, 1H), 2.56 (d, J = 7.8Hz, 2H), 1.50 (m, 2H), 1.32 (m, 6H), 0.90 (t, J = 6 .8Hz, 3H).

Synthesis Example 18 (Synthesis of bi(7-bromo-3-fluoro-6-hexyl-2-biphenylenyl)) (Step D7)
In a nitrogen atmosphere, 170 mg (0.412 mmol) of 2,7-dibromo-3-fluoro-6-hexylbiphenylene synthesized in Synthesis Example 17 and 10 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reactor. The solution was cooled to −10° C. and 0.70 ml (1.4 mmol) of THF solution of isopropylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at -10°C for 70 minutes to prepare 7-bromo-3-fluoro-6-hexylbiphenylenyl-2-magnesium chloride. Here, 183 mg (1.36 mmol) of copper (II) chloride (Wako Pure Chemical Industries) was added at 0°C. The resulting mixture was stirred overnight while gradually warming to room temperature. After adding 1M hydrochloric acid to the reaction mixture, toluene was added to separate the phases. The organic phase was washed twice with brine, dried over anhydrous sodium sulfate, and the organic phase was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane) to obtain 66.4 mg of a yellow solid of bi(7-bromo-3-fluoro-6-hexyl-2-biphenylenyl) (yield 48. 5%).

¹ H NMR (CDCl ₃ ): δ = 6.79 (s, 2H), 6.57 (s, 2H), 6.56-6.50 (m, 4H), 2.56 (d, J = 7 .8Hz, 4H), 1.52 (m, 4H), 1.31 (m, 12H), 0.90 (t, J = 6.8Hz, 6H).

Synthesis Example 19 (Synthesis of bi(3-fluoro-6-hexyl-2-biphenylenyl)) (Step E7)
Under a nitrogen atmosphere, 33.1 mg (0.0498 mmol) of bi(7-bromo-3-fluoro-6-hexyl-2-biphenylenyl) synthesized in Synthesis Example 18 and 3 ml of THF (dehydrated grade) were placed in a 50 ml Schlenk reaction vessel. added. This solution was cooled to −78° C., and 0.110 ml (0.176 mmol) of a hexane solution of n-butyllithium (1.6 M, Tokyo Chemical Industry Co., Ltd.) was added dropwise. After warming the mixture to −50° C. over 1 hour, 0.5 ml of methanol was added to quench the reaction. Water and toluene were added to the resulting reaction mixture and the phases were separated. The organic phase was washed with water and saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent; hexane/toluene = 1/0 to 9/1) to obtain 15.2 mg of a yellow solid of bi(3-fluoro-6-hexyl-2-biphenylenyl). (Yield 60.2%).

¹ H NMR (CDCl ₃ ): δ = 6.59 (d, J = 7.2 Hz, 2H), 6.56 (s, 2H), 6.54 (d, J = 6.8 Hz, 2H), 6 .52 to 6.50 (m, 2H), 6.48 to 6.46 (m, 2H), 2.41 (t, J = 7.6Hz, 4H), 1.58 to 1.50 (m, 4H), 1.31-1.26 (m, 12H), 0.89 (t, J=7.2Hz, 6H).

Example 9 Synthesis of (aromatic compound (1-21a, R ¹⁷ =C ₆ H ₁₃ )) (step F7)
Under a nitrogen atmosphere, in a 50 ml Schlenk reaction vessel, 15.2 mg (0.0300 mmol) of bi(3-fluoro-6-hexyl-2-biphenylenyl) synthesized in Synthesis Example 19, sodium sulfide nonahydrate (Wako Pure Chemical Industries, Ltd. Industry) 24.9 mg (0.104 mmol) and NMP (Wako Pure Chemical Industries) 3 ml. The mixture was heated to 170° C. and stirred for 4 hours. The resulting reaction mixture was ice-cooled and then quenched with water and 1N hydrochloric acid. The obtained orange suspension reaction liquid was suction-filtered, and the filtered solid was rinsed and washed with water, cold methanol, and cold hexane successively. The resulting residue was purified by recrystallization from hexane/toluene=6/4 to obtain 10.3 mg of yellow solid compound 7 (1-21a) (yield 68.6%).

MS (APCI ⁺ ) m/z: 501 (M ⁺ +H).

¹ H NMR (THF-d ₈ , 50° C.): δ=7.21 (s, 2H), 7.00 (s, 2H), 6.67-6.62 (m, 6H), 2.45 ( t, J = 7.6Hz, 4H), 1.62 ~ 1.55 (m, 4H), 1.38 ~ 1.30 (m, 12H), 0.90 (t, J = 7.0Hz, 6H ).

The HOMO level was -5.16 eV from the CV measurement.

Example 10 (Preparation of Solution for Forming Organic Semiconductor Layer)
Under air, 0.87 mg of 2,7-dihexyldithienobiphenylene (1-1a, compound 1) synthesized in Example 1 and 434 mg of toluene (Wako Pure Chemical Industries, Ltd., pure grade) were added to a 10 ml sample tube. After heating and dissolving at °C, the solution was allowed to cool 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.degree.

Example 11 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor)
Under air, the solution for forming an organic semiconductor layer obtained in Example 10 was applied on a highly doped n-type silicon substrate (Miyoshi, resistance value: 0.004Ω, with a silicon oxide film of 200 nm on the surface) with a diameter of 2 inches. The syringe-filled, 0.2 μm filtered solution was drop-cast under air. It was air-dried at room temperature (25° C.) to prepare a thin film of an aromatic compound (compound 1) with a film thickness of 56 nm.

A shadow mask having a channel length of 50 μm and a channel width of 500 μm was placed on the organic semiconductor layer, and gold was vacuum-deposited to form source and drain electrodes, thereby fabricating a bottom-gate/top-contact p-type organic thin film transistor.

Using a semiconductor parameter analyzer (Keithley 4200SCS), the electrical properties of the fabricated organic thin film transistor are scanned at the drain voltage (Vd = -50 V) and the gate voltage (Vg) from +5 to -70 V in increments of 1 V to evaluate the transfer characteristics. did The hole carrier mobility was 0.31 cm ² /V·sec, and the current on/off ratio was 2.0×10 ⁶ .

Further, the electrical properties of this organic thin film transistor were measured after annealing at 150° C. for 15 minutes. The hole carrier mobility was 0.33 cm ² /V·sec, the current on/off ratio was 1.9×10 ⁶ , and almost no deterioration in performance due to the heat treatment was observed.

Example 12 (Preparation of Solution for Forming Organic Semiconductor Layer)
A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 10, except that 0.43 mg of 2,7-dihexyldithienobiphenylene (1-3a, compound 2) synthesized in Example 2 was used. . The solution state was maintained even after 10 hours at 25.degree.

Example 13 (Preparation of organic semiconductor layer and organic thin film transistor)
Using the organic semiconductor layer forming solution obtained in Example 12, a thin film of an aromatic compound (compound 2) having a thickness of 29 nm was produced in the same manner as in Example 11, and a bottom gate-top contact type p type organic thin film transistors were fabricated.

As a result of evaluating the transfer characteristics of the transistor element, the hole carrier mobility was 0.23 cm ² /V·sec and the current on/off ratio was 1.0×10 ⁶ .

Further, the electrical properties of this organic thin film transistor were measured after annealing at 150° C. for 15 minutes. The hole carrier mobility was 0.22 cm ² /V·sec, the current on/off ratio was 1.0×10 ⁶ , and almost no deterioration in performance due to the heat treatment was observed.

Example 14 (Preparation of Solution for Forming Organic Semiconductor Layer)
A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 10, except that 0.88 mg of 2,7-dioctyldithienobiphenylene (1-1a, compound 3) synthesized in Example 3 was used. . The solution state was maintained even after 10 hours at 25° C. (the concentration of compound 3 was 0.20% by weight), confirming that the compound is suitable for film formation by drop casting and inkjet.

Example 15 (Preparation of organic semiconductor layer and organic thin film transistor)
Using the organic semiconductor layer forming solution obtained in Example 14, a top-gate/bottom-contact p-type organic thin film transistor was fabricated. Table 1 shows the material and film formation method of each component. The film thickness of the thin film of the aromatic compound (compound 3) was 58 nm.

As a result of evaluating the transfer characteristics of the transistor element, the hole carrier mobility was 0.60 cm ² /V·sec and the current on/off ratio was 3.0×10 ⁶ .

Further, the electrical properties of this organic thin film transistor were measured after annealing at 130° C. for 15 minutes. The hole carrier mobility was 0.58 cm ² /V·sec, the current on/off ratio was 2.8×10 ⁶ , and almost no deterioration in performance due to the heat treatment was observed.

Example 16 (Production of organic semiconductor layer and organic thin film transistor)
Using the solution for forming an organic semiconductor layer obtained in Example 14, and using the material of each constituent member and the film formation method shown in Example 15, a bottom gate-bottom contact type p-type organic thin film transistor was produced. The thickness of the thin film of the biphenylene derivative (compound 3) was 55 nm.

As a result of evaluating the transfer characteristics of the transistor element, the hole carrier mobility was 0.33 cm ² /V·sec and the current on/off ratio was 1.5×10 ⁶ .

Further, the electrical properties of this organic thin film transistor were measured after annealing at 130° C. for 15 minutes. The hole carrier mobility was 0.31 cm ² /V·sec, the current on/off ratio was 1.3×10 ⁶ , and almost no deterioration in performance due to the heat treatment was observed.

Comparative example 1
(Preparation of Solution for Forming Organic Semiconductor Layer)
An organic semiconductor layer-forming solution was prepared in the same manner as in Example 10 using 2,7-dioctylbenzothienobenzothiophene (Sigma-Aldrich) in a 10 ml sample tube under air. The compound remained in the solution state (0.20% by weight) even after 10 hours at 25°C, confirming that it is a compound suitable for film formation by drop casting and inkjet.

(Preparation of organic semiconductor layer and organic thin film transistor)
Using the solution for forming an organic semiconductor layer, a thin film of 2,7-dioctylbenzothienobenzothiophene having a film thickness of 60 nm was produced in the same manner as in Example 11, and a bottom gate-top contact p-type organic thin film transistor was produced. made.

As a result of evaluating the transfer characteristics of the transistor element, the hole carrier mobility was 0.01 cm ² /V·sec and the current on/off ratio was 3.0×10 ⁵ .

Further, the electrical properties of this organic thin film transistor were measured after annealing at 150° C. for 15 minutes. As a result, no transistor operation was obtained, and a significant deterioration in performance due to the heat treatment was observed. Microscopic observation confirmed that the organic semiconductor layer was destroyed by heating.

Comparative example 2
(Preparation of organic semiconductor layer and organic thin film transistor)
The same operation as in Comparative Example 1 was repeated except that the organic thin film transistor produced in Comparative Example 1 was annealed at 130° C. for 15 minutes. As a result, no transistor operation was obtained, and a significant deterioration in performance due to the heat treatment was observed. Microscopic observation confirmed that the organic semiconductor layer was destroyed by heating.

The aromatic compound of the present invention can be expected to be applied as a semiconductor device material typified by an organic thin film transistor because it provides high carrier mobility and is excellent in heat resistance and solubility.

(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 (5)

A biphenylene derivative which is an aromatic compound represented by the following general formula (7) .

[(Here, among combinations consisting of two adjacent R ¹ to R ⁸ , only one set of combinations consisting of two adjacent R ¹ to R ⁴ and adjacent R ⁵ to R ⁸ Only one of the two combinations constitutes the general formula (8).R ¹ to R ⁸ that do not constitute the following general formula (8) are each independently hydrogen, halogen, or carbon number 1 to 20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, or C4 to C26 aryl group.)

(Here, X represents oxygen, sulfur, or selenium, and Y represents CR ¹³ or nitrogen. R ⁹ and R ¹³ are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 4 to 26 carbon atoms.)] 2. The biphenylene derivative according to claim 1 ^, wherein ^R1 and ^R2 and R5 and R6 constitute the general formula ( ⁸ ). A solution for forming an organic semiconductor layer, comprising the biphenylene derivative according to claim 1 or 2 . An organic semiconductor layer formed by using the solution for forming an organic semiconductor layer according to claim 3 . An organic thin film transistor comprising the organic semiconductor layer according to claim 4 .

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