JP6047261B2 - Compound, organic semiconductor material containing the same, organic semiconductor ink, and organic transistor - Google Patents

Description

The present invention relates to a compound having a mesogenic skeleton, an organic semiconductor material containing the compound, an organic semiconductor ink, and an organic transistor.

Conventionally, a thin film transistor (TFT) using amorphous silicon or polycrystalline silicon has been widely used as a switching element for liquid crystal display devices, organic EL display devices and the like. However, since the CVD apparatus used for manufacturing these TFTs using silicon is expensive, manufacturing a large TFT element causes an increase in manufacturing cost. In addition, since a silicon material is formed at a high temperature, it cannot be applied to plastic substrates, which are flexible display substrate candidates, due to heat resistance problems. In order to solve this problem, an organic TFT using an organic semiconductor material for a channel (semiconductor layer) instead of a silicon semiconductor has been proposed.

  Organic semiconductor materials can be printed and formed at low temperatures by converting them into inks, so they do not require large-scale manufacturing facilities and can be applied to plastic substrates with poor heat resistance, and are expected to be applied to flexible electronics. Yes. On the other hand, organic semiconductor materials have lower semiconductor characteristics (mobility) than silicon semiconductors, and as a result, the response speed of TFTs has been a problem for practical use, but in recent years it has surpassed the mobility of amorphous silicon. Organic semiconductor materials have been developed.

For example, Patent Document 1 discloses a compound having a dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene skeleton (hereinafter, dinaphthothienothiophene is abbreviated as DNTT). Has been reported to exhibit a mobility of ˜4.0 cm ² / Vs in vacuum deposited films.

Furthermore, Patent Document 2 discloses a compound having a V-shaped structure having various substituents, and a coating film formed by a special method called an edge casting method has a high mobility of ˜11 cm ² / Vs. In addition, Patent Document 3 reports that a phenyl-substituted naphthodichalcogen compound exhibits a mobility of ˜0.7 cm ² / Vs, and the like, and the mobility of amorphous silicon (˜0.5 cm ² / Vs) is reported. ) There are many reports of materials exceeding. This is a result obtained by employing a molecule with expanded π-conjugate and producing a homogeneous organic semiconductor film so as to secure a carrier flow path.
On the other hand, Patent Document 4 discloses an anthracene derivative having a phenylethynyl group, but its mobility is ˜0.1 cm ² / Vs. By simply expanding the conjugated system, high mobility cannot be obtained, suggesting that molecular design for arranging π conjugates is necessary so that a carrier channel can be secured.

  Thus, although the mobility of organic semiconductors is increasing, there are still many problems to be obtained in order to obtain a high mobility semiconductor film by printing film formation. First, as described above, a compound having a high mobility is a polycyclic aromatic compound, and therefore has poor solvent solubility necessary for ink production. Secondly, many of the compounds have poor wet film-forming properties, and the film of the compound formed by a wet method cannot obtain high mobility such as partial crystallization. In particular, it has been difficult to achieve high mobility in a film formed by “casting of droplets and drying thereof”, which is a practical printing method such as an inkjet method or a nozzle printing method.

  On the other hand, for organic semiconductor materials made of a compound exhibiting a liquid crystal phase, it has been found that a semiconductor film formed through a liquid crystal phase exhibits a high mobility far exceeding that of an amorphous organic semiconductor material in recent years. Has been. In particular, Patent Document 5 discloses a material having a higher-order liquid crystal phase close to a crystal phase, and an organic semiconductor film having high alignment order is obtained, and therefore it indicates high mobility.

International Publication No. 2012/115236 Pamphlet International Publication No. 2013/125599 Pamphlet International Publication No. 2010/058692 Pamphlet International Publication No. 2009/125721 Pamphlet International Publication No. 2012/121393 Pamphlet

  Since conventional materials have poor solubility in solvents, it has been difficult to prepare inks such as precipitation of compounds at room temperature. In addition, in order to obtain high mobility such as disorder of molecular arrangement or partial crystallization during film formation by a wet method, it is necessary to arrange molecules by complicated heat treatment or a special film formation method.

  Therefore, an object of the present invention is to provide a film with high mobility, which has excellent solubility in a solvent and can be easily obtained without going through a complicated process (that is, only by casting ink droplets and drying them). The object is to provide a compound to be provided, and an organic semiconductor material using the compound, and to provide an organic semiconductor ink capable of easily producing an organic transistor having a practical configuration.

  In the present invention, as a result of intensive studies, a compound comprising a mesogen skeleton having a specific substituent has suitability as an organic semiconductor ink because of its excellent solvent solubility, and does not require complicated heat treatment and is simple. We have found that even if it is a wet method (that is, only a method of “casting ink droplets and drying them”), an organic semiconductor film having a uniform and high mobility can be formed, and the present invention has been completed. It was.

  ADVANTAGE OF THE INVENTION According to this invention, the compound which is excellent in the solubility to a solvent, and shows high mobility, the organic-semiconductor material containing this compound, organic-semiconductor ink, and an organic transistor can be provided.

It is a conceptual diagram of a top contact type transistor. It is a conceptual diagram of a bottom contact type transistor.

That is, the present invention includes the following items.
1. A compound represented by the general formula (1),

(R ₁ represents an aromatic hydrocarbon group or a heteroaromatic cyclic group, and one or two or more hydrogen atoms in the aromatic hydrocarbon group and the heteroaromatic cyclic group are acyclic or cyclic. The alkyl group having 1 to 20 carbon atoms in the formula, a halogeno group, an aromatic hydrocarbon group, a heteroaromatic ring group, or a nitrile group may be substituted, and the alkyl group is one of the alkyl groups or Two or more —CH ₂ — are optionally —O—, —CH═CH—, —CO—, —OCO—, —COO—, so that an oxygen atom, sulfur atom and nitrogen atom are not directly adjacent to each other. _{-S -, - sO 2 -,} - sO -, - NH -, - NR'- or -C≡C- may be substituted with, one or more hydrogen atoms in the alkyl group optionally May be substituted by a halogeno group or a nitrile group (provided that R ′ has 1 to 20 carbon atoms) Represents an acyclic or cyclic alkyl group).
R ₂ represents a phenylene group (—C ₆ H ₄ —), and p represents an integer of 0 or 1.
MSG
(A) Mesogenic skeleton selected from general formulas (2) to (10) (except for aromatic hydrocarbon, chemical formula (11), chemical formula (13), thienothiophene, dithienothiophene, and terthiophene) )
Or
(B) a mesogenic skeleton selected from the group consisting of chemical formula (11), thienothiophene, dithienothiophene, terthiophene, and general formula (12),
MSG is (a) a mesogen skeleton selected from general formulas (2) to (10) (however, aromatic hydrocarbon, chemical formula (11), chemical formula (13), thienothiophene, dithienothiophene, and terthiophene). In the case of), one of the hydrogen atoms of the MSG is substituted with a R ₁ —C≡C— (R ₂ ) _p — group, and the other hydrogen atoms are halogeno groups, acyclic groups Alternatively, it may be substituted with a cyclic alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms as a substituent, or a nitrile group. One or more —CH ₂ — is optionally —O—, —CH═CH—, —CO—, —OCO—, —, such that the oxygen, sulfur and nitrogen atoms are not directly adjacent. COO-, -S-,- _{O 2 -, - SO -,} - NH -, - NR'- or -C≡C- may be substituted with, one or more hydrogen atoms are optionally halogeno group or a nitrile group in the alkyl group (Wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms),
When MSG is a mesogenic skeleton selected from the group consisting of (b) chemical formula (11), thienothiophene, dithienothiophene, terthiophene, and general formula (12), one of the two terminal rings In which the hydrogen atom of the other ring is substituted with an R ₁ —C≡C— (R ₂ ) _p — group, and the hydrogen atom of the other ring is an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, carbon An aromatic hydrocarbon group which may be substituted with an alkyl group having 2 to 20 atoms, or a heteroaromatic ring group which may be substituted with an alkyl group having 2 to 20 carbon atoms, The other hydrogen atom is an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group which may be substituted with an alkyl group having 2 to 20 carbon atoms, or 2 to 2 carbon atoms. Substituted with 20 alkyl groups Good heteroaromatic ring group, a trialkylsilyl ethynyl group may be substituted with halogeno group or a nitrile group, one or more -CH 2 in the alkyl group _- is optionally an oxygen atom, as sulfur atom and nitrogen atoms are not directly adjacent, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - S -, - sO 2 -, - sO -, - NH- , —NR′— or —C≡C—, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogeno group or a nitrile group (provided that R 'Represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms). )

(K and l are each independently an integer of 0 to 3, X represents a chalcogen atom, and Ar is a tetravalent group forming a condensed ring selected from formulas (14) to (51).)

(L and X are as defined above.)
2.1. An organic semiconductor material containing the compound described in 1.
3.1. An organic semiconductor ink containing the compound described in 1.
4.2. An organic semiconductor device using the organic semiconductor material described in 1.
5.2. An organic transistor using the organic semiconductor material described in 1.

(Compound represented by the general formula (1))
The compound represented by the general formula (1) is a compound in which a triple bond (acetylene moiety) is bonded to a mesogen skeleton having a specific structure via a single bond or a phenylene group. The mesogenic skeleton has a feature that is a group represented by the general formulas (2) to (12).
_{Further, R} 1, _R 2, p and MSG (mesogen groups) of the present compounds represent the following, respectively.

R ₁ represents an aromatic hydrocarbon group or a heteroaromatic cyclic group, and one or two or more hydrogen atoms in the aromatic hydrocarbon group and the heteroaromatic cyclic group are acyclic or cyclic. The alkyl group may be substituted with an alkyl group having 1 to 20 carbon atoms, a halogen atom, an aromatic hydrocarbon group, a heteroaromatic ring group, or a nitrile group, and the alkyl group is one or two of the alkyl groups. The above —CH ₂ — is optionally —O—, —CH═CH—, —CO—, —OCO—, —COO—, —S, so that the oxygen atom, sulfur atom and nitrogen atom are not directly adjacent to each other. —, —SO ₂ —, —SO—, —NH—, —NR′— or —C≡C— may be substituted, and one or more hydrogen atoms in the alkyl group are optionally halogen atoms. Or may be substituted by a nitrile group (provided that R ′ has 1 to 20 carbon atoms) It represents an acyclic or cyclic alkyl group).

R ₂ represents a phenylene group (—C ₆ H ₄ —).

P represents an integer of 0 or 1.

Furthermore, MSG is a mesogenic skeleton selected from the general formulas (2) to (12),
When MSG is (2) to (10) (except for the case of aromatic hydrocarbon, chemical formula (11), chemical formula (13), tinothiophene, dithienothiophene, and terthiophene), One of the hydrogen atoms is substituted with a R ₁ —C≡C— (R ₂ ) _p — group, and the other hydrogen atoms are halogeno groups, acyclic or cyclic carbon atoms having 1 to 20 carbon atoms. It may be substituted with an alkyl group, an aromatic hydrocarbon group having a C 1-20 alkyl group as a substituent, or a nitrile group, and one or more —CH ₂ — in the alkyl group but optionally, an oxygen atom, such sulfur atoms and nitrogen atoms are not directly adjacent, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - S -, - sO 2 - , -SO-, -NH-, -NR'- May be substituted with —C≡C—, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogeno group or a nitrile group (where R ′ is the number of carbon atoms) 1 to 20 acyclic or cyclic alkyl groups)

In addition, when MSG is a mesogenic skeleton selected from the group consisting of chemical formula (11), thienothiophene, dithienothiophene, terthiophene, and general formula (12), A hydrogen atom is substituted with a R ₁ —C≡C— (R ₂ ) _p — group, and the hydrogen atom of the other ring is an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, a carbon atom Substituted with an aromatic hydrocarbon group which may be substituted with an alkyl group of 2 to 20 or a heteroaromatic ring group which may be substituted with an alkyl group of 2 to 20 carbon atoms, and others Is a non-cyclic or cyclic alkyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group which may be substituted with an alkyl group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. Substituted with an alkyl group of Good heteroaromatic ring group, a trialkylsilyl ethynyl group may be substituted with halogeno group or a nitrile group, one or more -CH 2 in the alkyl group _- is optionally an oxygen atom, as sulfur atom and nitrogen atoms are not directly adjacent, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - S -, - sO 2 -, - sO -, - NH- , —NR′— or —C≡C—, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogeno group or a nitrile group (provided that R 'Represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms).

First, R ₁ will be described. R ₁ represents an aromatic hydrocarbon group or a heteroaromatic cyclic group, and one or more hydrogen atoms thereof are an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, a halogeno group, a phenyl group An aromatic hydrocarbon group such as a group or naphthyl group, a heteroaromatic ring group such as a thienyl group, a furyl group or a pyrrolyl group, or a nitrile group, and the alkyl group is one of the alkyl groups. Or two or more —CH ₂ — are optionally —O—, —CH═CH—, —CO—, —OCO—, —COO— so that the oxygen, sulfur and nitrogen atoms are not directly adjacent. , —S—, —SO ₂ —, —SO—, —NH—, —NR′— or —C≡C—, wherein one or more hydrogen atoms in the alkyl group are optional. May be substituted with a halogen atom or a nitrile group. R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms).

Specifically, the aromatic hydrocarbon group or heteroaromatic ring group in R ₁ is (A-1) an unsubstituted aromatic hydrocarbon group or heteroaromatic ring group, or (A-2) a halogenated aromatic group. A hydrocarbon group or a heteroaromatic ring group, (A-3) an aromatic hydrocarbon group or a heteroaromatic ring group in which an aromatic hydrocarbon group or a heteroaromatic ring group is linked by a single bond, (A-4) a nitrile Aromatic hydrocarbon group or heteroaromatic ring group, (A-5) a linear or branched alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 1 to 20 carbon atoms, (A-6) C3-C20 alicyclic alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-7) C1-C19 alkoxy group-substituted aromatic hydrocarbon group or heteroaromatic group A ring group, (A-8) a C2-C19 alkoxyalkyl group-substituted fragrance Aromatic hydrocarbon group or heteroaromatic ring group, (A-9) alkenyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 2 to 20 carbon atoms, (A-10) 2 to 20 carbon atoms An alkanoyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-11) an alkanoylalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 3 to 20 carbon atoms, (A-12 ) C2-C20 alkoxycarbonyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-13) C2-C20 alkanoyloxy group-substituted aromatic hydrocarbon group or heteroaromatic group Aromatic ring group, (A-14) C1-C19 alkylsulfanyl group-substituted aromatic hydrocarbon group or heteroaromatic cyclic group, (A-15) C2-C19 alkylsulfanylalkyl group substitution Aromatic hydrocarbon group or heteroaromatic ring group, (A-16) alkylsulfonyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 1 to 19 carbon atoms, (A-17) 2 carbon atoms 19 to 19 alkylsulfonylalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-18) an alkylsulfinyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 1 to 19 carbon atoms, (A-19) C2-C19 alkylsulfinylalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-20) C1-C19 alkylamino group-substituted aromatic carbon group Hydrogen group or heteroaromatic ring group, (A-21) alkylaminoalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 2 to 19 carbon atoms, (A-22) 2 to 20 carbon atoms An alkynyl group-substituted aromatic hydrocarbon group or a heteroaromatic ring group.

Among the above R ₁ , from the viewpoint of improving the film forming property and mobility, the aromatic hydrocarbon group and the heteroaromatic ring group in R ₁ are (A-1) an unsubstituted aromatic hydrocarbon group or a heteroaromatic group. Aromatic ring group, (A-2) halogenated aromatic hydrocarbon group or heteroaromatic ring group, (A-3) aromatic hydrocarbon group in which aromatic hydrocarbon group or heteroaromatic ring group is linked by a single bond Or a heteroaromatic ring group, (A-5) a linear or branched alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 1 to 20 carbon atoms, or (A-6) a carbon number having 1 to 20 carbon atoms. An alicyclic alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-7) an alkoxy group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 1 to 19 carbon atoms, (A- 8) C2-C19 alkoxyalkyl group-substituted aromatic hydrocarbon group or complex Aromatic ring group, (A-9) C2-C20 alkenyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-14) C1-C19 alkylsulfanyl group-substituted Aromatic hydrocarbon group or heteroaromatic ring group, (A-15) C2-C19 alkylsulfanylalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-20) carbon atom number 1-19 alkylamino group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-21) alkylaminoalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 2-19 carbon atoms (A-22) an alkynyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 2 to 20 carbon atoms is preferred,
In order to obtain a compound with higher mobility, (A-1) an unsubstituted aromatic hydrocarbon group or heteroaromatic ring group, (A-2) a halogenated aromatic hydrocarbon group or heteroaromatic ring group, (A-3) An aromatic hydrocarbon group or heteroaromatic ring group in which aromatic hydrocarbon groups or heteroaromatic ring groups are linked by a single bond, (A-5) straight chain or branched having 1 to 20 carbon atoms An alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-6) an alicyclic alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group having 1 to 20 carbon atoms, (A-7) ) C1-C19 alkoxy group-substituted aromatic hydrocarbon group or heteroaromatic ring group, (A-8) C2-C19 alkoxyalkyl group-substituted aromatic hydrocarbon group or heteroaromatic group More preferably, it is a cyclic group.

In the more preferable structure of R ₁ described above, the linear or branched alkyl group having 1 to 20 carbon atoms includes methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and 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-tetradecyl group, n-pentadecyl group, n-hexadecyl group A linear alkyl group such as a group, n-heptadecyl group, n-octadecyl group, n-eicosyl group;
Isopropyl group, isobutyl group, isopentyl group, neopentyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, cyclohexylmethyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 3-ethylheptyl group, 2-propylpentyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5 , 5-trimethylhexyl group, 1-methyldecyl group, 1-hexylheptyl group and other branched alkyl groups.

  Examples of the alicyclic alkyl group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the alkoxy group having 1 to 19 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyl Examples thereof include an oxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a hexadecyloxy group, and a stearyloxy group.

Furthermore, as an alkoxyalkyl group having 2 to 19 carbon atoms, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-propoxyethyl group, a 2-isopropoxyethyl group, a 2-n-butoxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2′-ethylhexyloxy) ethyl Group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3 -Ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-n-pe Tyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2′-ethylbutoxy) propyl group, 3-n-octyloxypropyl group, 3- (2′-ethylhexyloxy) propyl group, 3-n -Decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl Group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxy Butyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 5-n-pentylo Cypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4- Methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxyoctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxy Decyl group, 10-ethoxydecyl group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetradecyl group, Cyclohexyloxyethyl group, cyclohexyloxypropyl group, etc. And so on.

Specific examples of the more preferable R ₁ described above include (A-1) an unsubstituted aromatic hydrocarbon group or heteroaromatic cyclic group, such as a phenyl group, a naphthyl group, an azulenyl group, an acenaphthenyl group, an anthranyl group, An unsubstituted monocyclic or polycyclic aromatic hydrocarbon group having 6 to 24 carbon atoms such as a phenanthryl group, a naphthacenyl group, a fluorenyl group, a pyrenyl group, a chrycenyl group, and a perylenyl group;
Pyrrolyl, indolyl, furyl, thienyl, imidazolyl, benzofuryl, triazolyl, benzotriazolyl, benzothienyl, pyrazolyl, indolizinyl, quinolinyl, isoquinolinyl, carbazolyl, dibenzofuranyl , Dibenzothiophenyl group, indolinyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, thiadiazinyl group, oxadiazolyl group, benzoquinolinyl group, thiadiazolyl group, pyrrolothiazolyl group, pyrrolopyridazinyl group, tetrazolyl group, oxazolyl An unsubstituted 5-membered or 6-membered heteroaromatic group, or a polycyclic heteroaromatic group obtained by condensing benzene to the heteroaromatic group;

  (A-2) Examples of the halogenated aromatic hydrocarbon group or heteroaromatic cyclic group include 4-fluorophenyl group, 2,6-fluorophenyl group, 4-chlorophenyl group, 2,3,4,5,6- The aromatic hydrocarbon group or heteroaromatic ring group such as a perfluorophenyl group, a fluoropyridinyl group, or a fluoroindolyl group is substituted with a halogeno group such as a fluoro group, a chloro group, a bromo group, or an iodo group Things.

  (A-3) An aromatic hydrocarbon group or heteroaromatic ring group in which an aromatic hydrocarbon group or a heteroaromatic ring group is linked by a single bond includes a biphenyl group, a terphenyl group, a binaphthyl group, a bipyridyl group, and a bithienyl. Group, terthienyl group, quaterthienyl group, kinktienyl group, sexthienyl group, furylphenyl group, thienylphenyl group and the like.

  (A-5) As a linear or branched alkyl group-substituted aromatic hydrocarbon group or heteroaromatic cyclic group having 1 to 20 carbon atoms, a tolyl group, a xylyl group, an ethylphenyl group, an n-propylphenyl group, Isopropylphenyl group, n-butylphenyl group, tert. -Butylphenyl group, n-pentylphenyl group, n-hexylphenyl group, n-heptylphenyl group, n-octylphenyl group, 2-ethylhexylphenyl group, n-decaphenyl group, stearylphenyl group, 5-methylthienyl group , 5-hexylthienyl group, 5-decathienyl group, 5-stearylthienyl group and the like.

  (A-6) C1-C20 alicyclic alkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group includes cyclohexylphenyl group, 4-methylcyclohexylphenyl group, 4-ethylcyclohexylphenyl group, etc. Is mentioned.

  (A-7) C1-C19 alkoxy group-substituted aromatic hydrocarbon group or heteroaromatic cyclic group is a methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group Pentyloxyphenyl group, hexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, decyloxyphenyl group, dodecyloxyphenyl group, stearyloxyphenyl group and the like.

(A-8) C2-C19 alkoxyalkyl group-substituted aromatic hydrocarbon group or heteroaromatic ring group includes 4- (2-ethoxyethyl) phenyl group, 4- (2-n -Hexyloxyethyl) phenyl group, 4- (2-n-heptyloxyethyl) phenyl group, 4- (2-n-tetradecyloxyethyl) phenyl group, 4- (2-cyclohexyloxyethyl) phenyl group, 4 -(12-ethoxydodecyl) phenyl group, 4- (cyclohexyloxyethyl) phenyl group, 5- (2-ethoxyethyl) thienyl group, 5- (2-n-tetradecyloxyethyl) thienyl group, 5- (2 -Cyclohexyloxyethyl) thienyl group, 5- (12-ethoxydodecyl) thienyl group, and the like.

Next, MSG (mesogenic group) of the compound represented by the general formula (1) of the present invention will be described. MSG is a mesogen skeleton selected from general formulas (2) to (10) (except for aromatic hydrocarbon, chemical formula (11), chemical formula (13), thienothiophene, dithienothiophene, and terthiophene). ), One of the hydrogen atoms of the MSG is substituted with an R ₁ —C≡C— (R ₂ ) _p — group, and the other hydrogen atoms are halogeno groups, acyclic or cyclic Which may be substituted with an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having an alkyl group having 1 to 20 carbon atoms as a substituent, or a nitrile group, Two or more —CH ₂ — are optionally —O—, —CH═CH—, —CO—, —OCO—, —COO—, so that an oxygen atom, sulfur atom and nitrogen atom are not directly adjacent to each other. -S -, - SO ₂ -, -SO-, -NH-, -NR'- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group are optionally substituted by a halogeno group or a nitrile group (Wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms),
When MSG is a mesogenic skeleton selected from the group consisting of chemical formula (11), thienothiophene, dithienothiophene, terthiophene, and general formula (12), a hydrogen atom in one of the two terminal rings Is substituted with a R ₁ —C≡C— (R ₂ ) _p — group, and the hydrogen atom of the other ring is an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, 2 carbon atoms An aromatic hydrocarbon group which may be substituted with an alkyl group of ˜20 or a heteroaromatic ring group which may be substituted with an alkyl group of 2 to 20 carbon atoms, and other hydrogen The atom is an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group which may be substituted with an alkyl group having 2 to 20 carbon atoms, or an alkyl having 2 to 20 carbon atoms. May be substituted with a group Containing aromatic ring group, a trialkylsilyl ethynyl group may be substituted with halogeno group or a nitrile group, one or more -CH 2 in the alkyl group _- is optionally an oxygen atom, a sulfur as atoms and nitrogen atoms are not directly adjacent, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - S -, - sO 2 -, - sO -, - NH-, -NR'- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group may be optionally substituted by a halogeno group or a nitrile group (provided that R ' Represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms).

  First, MSG is a mesogen skeleton selected from general formulas (2) to (10) (provided that aromatic hydrocarbon, chemical formula (11), chemical formula (13), thienothiophene, dithienothiophene, and terthiophene). Specifically, it can be exemplified by Chemical Formula 17 to Chemical Formula 19. However, in Chemical Formulas 17 to 19, X represents an oxygen atom, a sulfur atom, or a selenium atom.

When the number of condensed rings of MSG (mesogen group) increases, the π conjugation tends to expand and the mobility tends to increase, but the solubility in a solvent decreases. Therefore, from the balance between mobility and solubility, the number of condensed rings of the mesogenic group is preferably 3-8, more preferably 4-7.

  In addition, when the mesogenic group contains a heteroaromatic ring, the mobility is increased by increasing the electron density, and the atmospheric stability of the resulting compound tends to be improved. Therefore, when the compound of the present invention is used as an organic semiconductor ink, the mesogenic group is particularly preferably a heteroaromatic ring group rather than an aromatic hydrocarbon group.

  In consideration of the above, a particularly preferred mesogen skeleton is specifically represented by Chemical Formula 20.

Further, a more preferred mesogen skeleton is represented by the following formula: from the viewpoint of the synthesis of the mesogen group skeleton and the ease of introducing the R ₁ -C≡C- group into one of the hydrogen atoms of the mesogen group for obtaining film-forming properties. It appears in.

In the mesogenic group as a constituent component of the compound of the present invention, one of the hydrogen atoms is substituted with an R ₁ —C≡C— (R ₂ ) _p — group, and other hydrogen atoms are It may be substituted with a halogeno group such as a fluoro group, a chloro group, a bromo group or an iodo group, a nitrile group, or an acyclic or cyclic alkyl group having 1 to 20 carbon atoms. Here, one or more —CH ₂ — in the alkyl group is optionally —O—, —CH═CH—, —, so that an oxygen atom, a sulfur atom and a nitrogen atom are not directly adjacent to each other. CO—, —OCO—, —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR′— or —C≡C— may be substituted. One or more hydrogen atoms may be optionally substituted with a halogeno group or a nitrile group (where R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms).

A substituent of the mesogenic group of the present invention, -CH ₂ - is -O -, - CH = CH - , - CO -, - OCO -, - COO -, - S -, - SO 2 -, - SO- , —NH—, —NR′—, or alkyl optionally substituted by —C≡C— is (B-1) a linear or branched alkyl group having 1 to 20 carbon atoms, (B-2) An alicyclic alkyl group having 3 to 20 carbon atoms, (B-3) an alkoxy group having 1 to 19 carbon atoms, (B-4) an alkoxyalkyl group having 2 to 19 carbon atoms, and (B-5) carbon atom. An alkenyl group having 2 to 20 carbon atoms, (B-6) an alkanoyl group having 2 to 20 carbon atoms, (B-7) an alkanoylalkyl group having 3 to 20 carbon atoms, and (B-8) 2 to 20 carbon atoms. Alkoxycarbonyl group, (B-9) alkanoyloxy group having 2 to 20 carbon atoms, (B-10) carbon 1 to 19 alkylsulfanyl groups, (B-11) alkylsulfanylalkyl groups having 2 to 19 carbon atoms, (B-12) alkylsulfonyl groups having 1 to 19 carbon atoms, and (B-13) carbon atoms An alkylsulfonylalkyl group having 2 to 19 carbon atoms, (B-14) an alkylsulfinyl group having 1 to 19 carbon atoms, (B-15) an alkylsulfinylalkyl group having 2 to 19 carbon atoms, and (B-16) carbon atom. An alkylamino group having 1 to 19 carbon atoms, (B-17) an alkylaminoalkyl group having 2 to 19 carbon atoms, and (B-18) an alkynyl group having 2 to 20 carbon atoms.

Among the above groups, in order to enhance the solubility of the compound represented by the general formula (1) of the present invention and improve the film forming property and mobility, (B-1) a straight chain having 1 to 20 carbon atoms. A chain or branched alkyl group, (B-2) an alicyclic alkyl group having 3 to 20 carbon atoms, (B-3) an alkoxy group having 1 to 19 carbon atoms, and (B-4) having 2 to 19 carbon atoms. An alkoxyalkyl group, (B-5) an alkenyl group having 2 to 20 carbon atoms, (B-10) an alkylsulfanyl group having 1 to 19 carbon atoms, and (B-11) an alkylsulfanylalkyl having 2 to 19 carbon atoms. Group or (B-18) an alkynyl group having 2 to 20 carbon atoms, and in order to obtain a compound with high mobility, the above group is (B-1) 1 to 20 carbon atoms. A linear or branched alkyl group of (B-3) having 1 to 19 carbon atoms Alkoxy group, particularly preferably (B-4) alkoxyalkyl group having a carbon number of 2 to 19.

Particularly preferred examples of the alkyl group include (B-1) a linear or branched alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an 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-tetradecyl group, n-pentadecyl group Linear alkyl groups such as n-hexadecyl group, n-heptadecyl group, n-octadecyl group and n-eicosyl group;
Isopropyl group, isobutyl group, isopentyl group, neopentyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, cyclohexylmethyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 3-ethylheptyl group, 2-propylpentyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5 Branched alkyl groups such as 1,5-trimethylhexyl group, 1-methyldecyl group, 1-hexylheptyl group;
Examples thereof include a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

(B-3) As the alkoxy group having 1 to 19 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, Examples include a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a hexadecyloxy group, and a stearyloxy group.

Further, (B-4) the alkoxyalkyl group having 2 to 19 carbon atoms includes 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n -Butoxyethyl group, 2-n-hexyloxyethyl group, 2- (2'-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2 ' -Ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3- Methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, -N-pentyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2'-ethylbutoxy) propyl group, 3-n-octyloxypropyl group, 3- (2'-ethylhexyloxy) propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n -Propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n -Dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 5-n- Nthyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group 4-methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxyoctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxydecyl group, 10-ethoxydecyl group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetra Decyl group, cyclohexyloxyethyl group, cyclohexyloxyp And a propyl group.

In addition, when MSG is a mesogenic skeleton selected from the group consisting of chemical formula (11), thienothiophene, dithienothiophene, terthiophene, and general formula (12), A hydrogen atom is substituted with a R ₁ —C≡C— (R ₂ ) _p — group, and the hydrogen atom of the other ring is an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, a carbon atom It is substituted with an aromatic hydrocarbon group which may be substituted with an alkyl group having 2 to 20 carbon atoms or a heteroaromatic ring group which may be substituted with an alkyl group with 2 to 20 carbon atoms.
Such an acyclic or cyclic alkyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group optionally substituted with an alkyl group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms Examples of the heteroaromatic cyclic group which may be substituted with an alkyl group include the groups described in the above (A-5), (A-6), and (B-1).

Next, R ₂ of the compound represented by the general formula (1) of the present invention is a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group, and p is 0 or 1 Is an integer. When p is 1, since the MSG and the phenylene group are linked to function as one charge transport unit, a compound with high mobility can be obtained even when the number of condensed rings of the MSG is small. . In order to obtain higher mobility, the phenylene group is preferably a 1,4-phenylene group. Further, when the MSG and the phenylene group are linked (that is, when p is 1), the number of condensed rings of MSG is preferably 2 to 7, and considering the balance between mobility and solubility, 3 to 6 More preferably it is.

  A preferred structure when MSG and a phenylene group are linked (that is, when p is 1) is Chemical Formula 22.

Also, synthesis of a mesogenic group skeleton and introduction of an R ₁ —C≡C— (R ₂ ) _p — group (when P = 1) into one of the hydrogen atoms of the mesogenic group to obtain film-forming properties. In view of the ease, a more preferred structure of the mesogen skeleton includes Chemical Formula 23.

  As described above, a preferable structure according to the present invention includes the following general formula (52).

(R ₃ represents an aromatic hydrocarbon group or a heteroaromatic cyclic group, and one or two or more hydrogen atoms in the aromatic hydrocarbon group and the heteroaromatic cyclic group are acyclic or cyclic. The alkyl group may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogeno group of the formula, and the alkyl group is optionally substituted with one or more —CH ₂ — in the alkyl group. The alkyl group may be substituted with —O—, —CH═CH—, —S—, —NH—, —NR ′, or —C≡C— so that the sulfur atom and the nitrogen atom are not directly adjacent to each other. One or more hydrogen atoms therein may be optionally substituted by a halogeno group or a nitrile group (wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms) .
MSG ′ is a mesogenic skeleton selected from the general formulas (2) to (10) or the general formula (11), thienothiophene, dithienothiophene, and terthiophene, and one of the hydrogen atoms of the MSG ′ is R ₃ —C≡C— (R ₂ ) _p — is substituted, and other hydrogen atoms may be substituted with an acyclic or cyclic alkyl group having 1 to 20 carbon atoms. , One or more —CH ₂ — in the alkyl group is optionally —O—, —CH═CH—, —S— so that the oxygen, sulfur and nitrogen atoms are not directly adjacent. , —NH—, —NR′— or —C≡C—, and one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogeno group or a nitrile group. (Where R ′ is an acyclic group having 1 to 20 carbon atoms or It represents a cyclic alkyl group).
R ₂ and p are as defined above. )

When the number of condensed rings of MSG 'increases, the π conjugation tends to expand and the mobility tends to increase, but the solubility in a solvent decreases. Therefore, from the balance between mobility and solubility, the number of condensed rings of the mesogenic group is preferably 2 to 7, and more preferably 3 to 6.

  In addition, when MSG ′ contains a heteroaromatic ring, the mobility is increased by increasing the electron density, and the atmospheric stability of the resulting compound tends to be improved. Therefore, when the compound of the present invention is used as an organic semiconductor ink, the MSG ′ is particularly preferably a heteroaromatic ring group rather than an aromatic hydrocarbon group.

  In view of the above, a particularly preferred MSG ′ skeleton is specifically represented by Chemical Formula 20 described above.

Further, more preferred mesogens are preferred because of the synthesis of the MSG ′ skeleton and the ease of introduction of the R ₃ —C≡C— (R ₂ ) _p group into one of the hydrogen atoms of MSG ′ for obtaining film forming properties. The skeleton is represented by Chemical Formula 21 described above.

  Furthermore, the compound of the present invention is particularly preferably a compound represented by the following general formula (53).

(R ₄ represents an aromatic hydrocarbon group or a heteroaromatic cyclic group, and one or two or more hydrogen atoms in the aromatic hydrocarbon group and the heteroaromatic cyclic group are acyclic or cyclic. The alkyl group may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogeno group of the formula, and the alkyl group is optionally substituted with one or more —CH ₂ — in the alkyl group. May be substituted with -O- so that they are not directly adjacent.
MSG ″ is a mesogenic skeleton selected from the general formulas (2) to (10) or the general formula (11), thienothiophene, dithienothiophene, and terthiophene, and among the hydrogen atoms of the MSG ″ One is substituted with an R ₄ —C≡C— (R ₂ ) _p — group, and at least one of the other hydrogen atoms is substituted with R ₅ .
R ₅ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, and one or two or more —CH ₂ — in the alkyl group is optionally not directly adjacent to an oxygen atom. And may be substituted with -O-. R ₂ and p are as defined above. )

As the number of condensed rings in MSG ″ increases, the π conjugation tends to expand and the mobility tends to increase, but the solubility in a solvent decreases. Therefore, from the balance between mobility and solubility, the number of condensed rings of the mesogenic group is preferably 2 to 7, and more preferably 3 to 6.

  In addition, when MSG ″ contains a heteroaromatic ring, the mobility is increased by increasing the electron density, and the atmospheric stability of the resulting compound tends to be improved. Accordingly, when the compound of the present invention is used as an organic semiconductor ink, the MSG ″ is particularly preferably a heteroaromatic ring group rather than an aromatic hydrocarbon group.

  In view of the above, a particularly preferred MSG ″ skeleton is specifically represented by Chemical Formula 20 described above.

Furthermore, from the ease of introduction of the R ₄ —C≡C— (R ₂ ) _p group into one of the hydrogen atoms of MSG ″ for synthesizing the MSG ″ skeleton and obtaining film-forming properties, A preferred MSG ″ skeleton is represented by Chemical Formula 21 described above.

  Furthermore, specific compounds of the present invention may include Chemical Formulas 26 to 29, but are not limited thereto.

(Synthesis of the compound of the present invention)
The compound of the present invention can be synthesized by a combination of known and commonly used methods.
An example of a synthetic route can include the following.

(Example of synthetic route)
In the case of the compound represented by (IV-2) in Chemical Formula 26 above, it can be synthesized by the scheme shown in Chemical Formula 30.

First, 1,5-dihydroxynaphthalene and a halogenating agent are reacted to obtain dihalogenodihydroxynaphthalene (4-2a).
Examples of the halogenating agent include chlorinating agents such as chlorine and sulfuryl chloride; brominating agents such as bromine, sodium N-bromoisocyanurate, N-bromosuccinic imide and N-bromophthalic imide; iodine and iodine chloride. And iodinating agents such as N-iodosuccinic imide, and the like can be used alone or in combination of two or more.
The amount of the halogenating agent used is not limited as long as the target dihalogen can be obtained, but is generally 1 to 50 equivalents relative to dihydroquinaphthalene, which increases the yield of the dihalogen. In order to suppress the by-product of a halogen body, 1.8-5 equivalent is preferable.
The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, and dibutyl ether, and esters such as ethyl acetate, isopropyl acetate, and amyl acetate. Solvents, aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, aromatics such as toluene, benzene, xylene Hydrocarbon solvents, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone, sulfur-containing solvents such as dimethyl sulfoxide, sulfolane, nitrile solvents such as acetonitrile, valeronitrile, benzonitrile, Acetic acid, Propionic acid, there may be mentioned carboxylic acid solvents such as butyric, these solvents may be used singly or in combination.

The reaction temperature is not particularly limited as long as the target dihalogen can be obtained. For example, the reaction temperature may be in the range of −20 ° C. to 200 ° C.
This reaction proceeds without using a catalyst, but catalysts such as iron powder, iron trichloride, iron tribromide, aluminum chloride, aluminum bromide, and iodine are used to shorten the reaction time and enhance the reaction selectivity. May be used. These catalysts can be used alone or in combination, and the amount used is not particularly limited, and may be, for example, 0.001 to 10 equivalents relative to the halogenating agent.

Subsequently, (4-2a) and an acylating agent are reacted to obtain diacyloxydihalogenonaphthalene (4-2b).
As the acylating agent, a carboxylic anhydride derived from a known carboxylic acid or a carboxylic acid halide can be used.
Examples of the carboxylic acid include acetic acid, n-propionic acid, n-butyric acid, n-valeric acid, n-hexanoic acid, n-heptanoic acid, i-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, n -Nonanoic acid, 3,5,5-trimethylhexanoic acid, n-decanoic acid, n-undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid and other fatty acids, benzoic acid, methylbenzoic acid Examples thereof include aromatic carboxylic acids such as acid and octylbenzoic acid.
The amount used is usually 1.5 to 50 equivalents relative to dihalogenodihydroquinaphthalene, and 2 to 5 equivalents are preferred in order to increase the reaction yield.
There is no restriction | limiting in particular as long as it is inactive to reaction, For example, the solvent of the said description can be used, These solvents may be used individually or in combination of 2 or more types.

The reaction temperature is not particularly limited as long as (4-2b) is obtained, and is, for example, -20 ° C to 200 ° C, preferably about 0 ° C to 150 ° C.
The reaction proceeds without using a catalyst, but a catalyst may be used to shorten the reaction time or improve the yield. Examples of the catalyst include trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene. Tertiary amines such as 1,4-diaza-bicyclo [2.2.2] octane, monoalkyl-substituted pyridines such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, t-butylpyridine, 2 , 3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2-methyl-5-ethyl-pyridine, 2,6-diisopropylpyridine Dialkylpyridines such as 2,6-di-tert-butylpyridine Include such pyridine derivatives, these catalysts can be used singly or in combination, the amount used may be an 0.001 equivalents to the acylating agent.

Next, diacyloxydihalogenonaphthalene and silylated terminal acetylene are subjected to Sonogashira coupling reaction in the presence of palladium catalyst, copper catalyst and amine to obtain bis (silylated ethynyl) acyloxynaphthalene (4-2c). .
Examples of the silylated terminal acetylene include trimethylsilylacetylene, triethylsilylacetylene, triisopropylsilylacetylene, etc., and the amount used is usually 1.5 to 50 equivalents relative to (4-2b), increasing the reaction yield. Therefore, 2 to 5 equivalents are preferable.
Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis [1,2-bis (diphenyl). Phosphino) ethane] palladium (0), bis (tri-t-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (0) and other zero-valent palladium compounds,
Dichlorobis (triphenylphosphine) palladium (II), allylpalladium (II) chloride dimer, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium (II), bis (triphenylphosphine) palladium (II) acetate, chloride (cis) , Cis-1,5-cyclooctanediene) palladium (II), palladium acetate (II) 2,4-acetylacetonate (II), palladium (II) chloride and the like. .
The said palladium catalyst can be used individually or in combination of 2 or more types, The usage-amount will not be restrict | limited especially if it is a range with which (4-2c) is obtained, It is 0.001 with respect to (4-2b). 10 equivalents.

Furthermore, in order to increase the activity of the palladium catalyst, a ligand may be used in combination.
Examples of the ligand include monodentate phosphine-based ligands such as trimethylphosphine, triethylphosphine, tri (n-butyl) phosphine, tri-t-butylphosphine, tricyclohexylphosphine, triphenylphosphine, and tri (o-tolyl) phosphine. Bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene, 1,1′-bis (diphenylphosphino) And bidentate phosphine-based ligands such as ferrocene.
The said ligand can be used individually or in combination of 2 or more types, and the usage-amount will not be restrict | limited especially if (4-2c) is obtained, For example, 0.1-0.1 with respect to a palladium catalyst. 10 equivalents.

Examples of the copper catalyst include copper iodide, copper bromide, copper chloride, copper acetate, copper trifluoroacetate, copper cyanide, copper trifluoromethanesulfonate, and the like. It may be used in combination of more than one species, and the amount used is not particularly limited as long as (4-2c) is obtained, and for example, 0.001 to 10 equivalents, preferably with respect to diacyloxydihalogenonaphthalene Is 0.01-1 equivalent.
Examples of amines include primary amines such as ammonia, methylamine, ethylamine, and propylamine, secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, morpholine, piperidine, and pyrrolidine, triethylamine, tributylamine, There may be mentioned tertiary amines such as diisopropylethylamine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza-bicyclo [2.2.2] octane.

The said amine can be used individually or in combination of 2 or more types, and there is no restriction | limiting in particular if the usage-amount is the range in which (4-2c) is obtained, 0.01 equivalent or more with respect to (4-2b) Any amine may be used as a reaction solvent. When amine is not used as a solvent, a solvent inert to the reaction can be used, and examples thereof include the various solvents described above.
The reaction temperature is not particularly limited as long as (4-2c) is obtained, and may be in the range of −20 ° C. to 200 ° C.

Next, (4-2c) is treated with a base to give unsubstituted dinaphthodifuran (4-2d). The base is not particularly limited as long as it has sufficient basicity to act on an acyl group. For example, carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide, water Hydroxides such as potassium oxide, cesium hydroxide, fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, n-butyl lithium, sec-butyl lithium, t-butyl lithium, isopropyl magnesium bromide, etc. An organic metal etc. are mentioned, These bases can be used individually or in combination of 2 or more types, The usage-amount will not be restrict | limited especially if (4-2d) is obtained, For example, (4- 1 to 100 equivalents relative to 2c), preferably 2 to 10 equivalents in order to increase the reaction yield.
The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include the solvents described above.
The reaction temperature is not particularly limited as long as (4-2d) can be obtained, and is, for example, −100 ° C. to 300 ° C., preferably about −80 ° C. to 200 ° C.

Subsequently, (4-2d) is orthometalated and then reacted with an alkylating agent to obtain monoalkyldinaphthodifuran (4-2e).
Examples of the orthometalation method include a method in which an organic metal such as n-butyllithium, sec-butyllithium, t-butyllithium, and isopropylmagnesium bromide is allowed to act. These may be used alone or in combination of two or more. Can be used.
The amount of the organic metal used is not particularly limited as long as (4-2e) can be obtained. For example, it is 0.5 to 3 equivalents relative to unsubstituted dinaphthodifuran to increase the yield of the monoalkyl compound. It is preferable that it is 0.8-1.6 equivalent.

Ortho metalation proceeds without using a catalyst, but a catalyst may be used to increase the yield. Examples of the catalyst include N, N, N ′, N′-tetramethylethylenediamine, hexamethylphosphoric triamide and the like, and these can be used alone or in combination of two or more thereof. If it is a range in which 2e) is obtained, it will not be restrict | limited, For example, it is 0.01-100 equivalent with respect to an organic metal.
Furthermore, reaction with an alkylating agent may be facilitated by adding a metal salt after orthometalation to perform metal exchange. Usable metal salts include zinc salts such as zinc chloride, zinc bromide and zinc iodide, copper salts such as copper chloride, copper bromide and copper iodide, tin chloride such as trimethyltin chloride and tributyltin chloride, etc. These may be added as a powder or may be added as a solution. The amount of the organic metal used is not particularly limited as long as (4-2e) can be obtained, but is generally equivalent to or more than the above orthometalating agent.
Examples of the alkylating agent include alkyl halides such as alkyl chloride, alkyl bromide and alkyl iodide, and sulfonic acid esters such as alkyl methanesulfonic acid ester and alkyl p-toluenesulfonic acid ester.
The amount of the alkylating agent used is not particularly limited as long as (4-2e) can be obtained, and is, for example, 1 to 10 equivalents, preferably 1 to 3 equivalents, relative to unsubstituted dinaphthodifuran.

The solvent is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, dibutyl ether, n-hexane, heptane, octane, cyclohexane, cyclohexane Examples thereof include aliphatic hydrocarbon solvents such as pentane and aromatic hydrocarbon solvents such as toluene, benzene and xylene.
The reaction temperature is not particularly limited as long as (4-2e) can be obtained, and is, for example, −100 ° C. to 200 ° C., preferably about −80 ° C. to 150 ° C.

Next, (4-2e) and a halogenating agent are reacted to obtain a monoalkylmonohalogenodinaphthodifuran (4-2f).
This reaction can be performed under the same conditions as the halogenation reaction of (4-2a) above.

Finally, (4-2f) and arylated terminal acetylene are subjected to Sonogashira coupling in the presence of a palladium catalyst, a copper catalyst, and an amine in the same manner as in the above (4-2c) to obtain the target (4-2). Can be obtained.

Examples of arylated terminal acetylene include ethynylbenzene, 4-methylethynylbenzene, 4-ethylethynylbenzene, 4-propylethynylbenzene, 4-butylethynylbenzene, 4-pentylethynylbenzene, and other alkylethynylbenzene, 4-methoxyethynylbenzene, Examples include alkoxyethynylbenzene such as 4-phenoxyethynylbenzene, heteroarylacetylene such as 2-pyridylacetylene, 3-pyridylacetylene, 2-thienylacetylene and 3-thienylacetylene.
The amount of the arylated terminal acetylene used is not particularly limited as long as (4-2) can be obtained, and is, for example, 1 to 10 equivalents, preferably 1 to 3 equivalents with respect to (4-2f).
In the synthesis method of (IV-2) in the above chemical formula 26, by using 1,5-dihydroxynaphthalene or 2,6-dihydroxynaphthalene as a starting material and performing a similar synthesis, it is shown in chemical formula 26 or chemical formula 27. (IV-1) to (IV-16) can be obtained.

  In addition, the dinaphthothienothiophene derivative (IV-18) exemplified in Chemical Formula 27 is a compound represented by (4-18d) and a compound represented by (4-18h), for example, according to the scheme represented by Chemical Formula 31. Can be obtained by coupling reaction.

In the synthesis of (4-18d) as one unit, first, alkoxyhalogenonaphthalene and Grignard reagent are reacted under a nickel catalyst to obtain alkoxyalkylnaphthalene (4-18a).
As the alkoxyhalogenonaphthalene, one obtained by substituting one alkoxy group and a halogen atom such as fluorine, chlorine, bromine or iodine at the beta position of each of the two benzene rings of naphthalene is used.

Examples of the alkoxy group include methoxy group, methoxymethoxy group, benzyloxymethoxy group, methoxyethoxymethoxy group, 2- (trimethylsilyl) ethoxymethyl group, methylthiomethyl group, phenylthiomethyl group, azidomethoxy group, cyanomethoxy group, t -A butyl diphenylsilyl ethoxy group, 2-tetrahydropyranyl ether group, etc. are mentioned.
As the Grignard reagent, commercially available Grignard reagents such as methylmagnesium chloride or bromide, ethylmagnesium chloride or bromide, isopropylmagnesium chloride or bromide, butylmagnesium chloride or bromide may be used, or prepared from an alkyl halide and metallic magnesium. It doesn't matter.
The amount of the Grignard reagent used is not particularly limited as long as (4-18a) can be obtained. For example, 0.5 to 10 equivalents relative to alkoxyhalogenonaphthalene, preferably 0.5 to increase the reaction yield. 9-3 equivalents.

Examples of the nickel catalyst include zero-valent nickel compounds such as nickel (0) powder, tetrakis (triphenylphosphine) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0);
Dichlorobis (triphenylphosphine) nickel (II), nickel chloride (II), nickel bromide (II), nickel iodide (II), nickel sulfate (II), nickel nitrate (II), nickel acetate (II), nickel (II) Acetylacetonate, dichloro [1,2-bis (diphenylphosphino) ethane] nickel (II), dichloro [1,2-bis (diphenylphosphino) propane] nickel (II), dichloro (tri-t -Butylphosphine) nickel (II), dichloro [1,2-bis (dicyclohexylphosphino) ethane] nickel (II), dichlorobis (tricyclohexylphosphine) nickel (II), dichloro (2,2'-bipyridyl) nickel ( II-valent nickel compounds such as II).
The nickel catalyst may be used alone or in combination of two or more, and the amount used is not particularly limited as long as (4-18a) can be obtained. For example, the nickel catalyst is 0 with respect to alkoxyhalogenonaphthalene. 0.005 to 50 equivalents, preferably 0.05 to 5 equivalents.

The solvent is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, dibutyl ether, n-hexane, heptane, octane, cyclohexane, cyclohexane Examples thereof include aliphatic hydrocarbon solvents such as pentane and aromatic hydrocarbon solvents such as toluene, benzene and xylene.
The reaction temperature is not particularly limited as long as (4-18a) can be obtained, and is, for example, -100 ° C to 200 ° C, preferably -80 ° C to 150 ° C.

Next, (3-18a) is orthometalated and then reacted with a thioalkylating agent to obtain thioalkoxyalkoxyalkylnaphthalene (4-18b).
For the orthometalation, the reagent (4-2e) and the synthesis conditions described above can be referred to.
The thioalkyl agent, such as dimethyl disulfide, diethyl disulfide, disulfides such as dipropyl disulfide;, S- methyl thiosulfonate, mention may be made of S- alkyl thiosulfonate such as S- methylphenyl thiosulfonate .
The amount of the thioalkylating agent to be used is not particularly limited as long as (4-18b) is obtained. For example, it is 0.5 to 100 equivalents, preferably 1 to 10 equivalents, relative to the alkoxyhalogenonaphthalene.

Subsequently, (4-18b) is reacted with a dealkylating agent to obtain thioalkoxyhydroxyalkylnaphthalene (4-18c).
As the dealkylation reaction, reference can be made to the 5th edition, Experimental Chemistry Course Vol. 14, pages 307-314 (Maruzen Co., Ltd.). Examples of the dealkylating agent include trimethylsilane bromide, trimethylsilane iodide, tetrachloride. Silicon reagents such as silicon-sodium iodide, methyl silicon trichloride-sodium iodide, boron trichloride, boron tribromide, aluminum chloride, hydrobromic acid, hydroiodic acid, trifluoroacetic acid and other Lewis acids, sodium Examples thereof include nucleophilic reagents such as methoxide, sodium thioethoxide, potassium thiophenoxide, and catalytic hydrogenation reagents such as H2 / Pd-C, H2 / Pd (OH) 2, and H2 / PdO2.
The amount of the dealkylating agent to be used is not particularly limited as long as (4-18c) is obtained, and for example, 0.5 to 100 equivalents, preferably 1 to 10 equivalents, relative to thioalkoxyalkoxyalkylnaphthalene. is there.
The solvent is not particularly limited as long as it is inert to the reaction. For example, an aliphatic hydrocarbon solvent such as n-hexane, heptane, octane, cyclohexane, cyclopentane, dichloromethane, chloroform, carbon tetrachloride, 1,2- (4-18c) is obtained as the reaction temperature, which can include halogenated solvents such as dichloroethane, aromatic hydrocarbon solvents such as toluene, benzene, and xylene, and nitrile solvents such as acetonitrile, valeronitrile, and benzonitrile. If it is conditions, it will not restrict | limit in particular, For example, it is -100 degreeC-200 degreeC, Preferably, it is about -80 degreeC-150 degreeC.

Next, (4-18c) is reacted with trifluoromethanesulfonic anhydride to give a thioalkoxyalkylnaphthyl triflate (4-18d).
The amount of trifluoromethanesulfonic anhydride used is not particularly limited as long as (4-18d) is obtained. For example, 1 to 100 equivalents, preferably 1 to 10 equivalents, with respect to thioalkoxyhydroxyalkylnaphthalene. is there.
Examples of the catalyst include trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene. Tertiary amines such as 1,4-diaza-bicyclo [2.2.2] octane, monoalkyl-substituted pyridines such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, t-butylpyridine, 2 , 3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2-methyl-5-ethyl-pyridine, 2,6-diisopropylpyridine Dialkylpyridines such as 2,6-di-tert-butylpyridine And the like can be used pyridine derivatives.

The said catalyst may be used individually or in combination of 2 or more types, and the usage-amount is 0.001-1000 equivalent with respect to trifluoromethanesulfonic anhydride, Preferably it is 0.01-100 equivalent.
Any solvent can be used as long as it is inert to the reaction. Examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, and dibutyl ether, n-hexane, heptane, and octane. , Aliphatic hydrocarbon solvents such as cyclohexane and cyclopentane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane, toluene , Aromatic hydrocarbon solvents such as benzene and xylene, and nitrile solvents such as acetonitrile, valeronitrile, and benzonitrile.
The reaction temperature is not particularly limited as long as (4-18d) is obtained, and is, for example, -20 ° C to 200 ° C, preferably 0 ° C to 150 ° C.

In the synthesis of (4-18h) as the other unit, first, alkoxyhalogenonaphthalene and arylated terminal acetylene are subjected to Sonogashira coupling reaction in the presence of a palladium catalyst, a copper catalyst and an amine, and then alkoxyaryl. Ethynylnaphthalene (4-18e) is obtained.
This reaction can be carried out under the same conditions as in the above reaction (4-2).

Next, (4-18e) is orthometalated and then reacted with a thioalkylating agent to give thioalkoxyalkoxyarylethynylnaphthalene (4-18f).
For this reaction, the above synthesis method (4-18b) can be referred to.

Subsequently, (4-18f) is reacted with a dealkylating agent to give thioalkoxyhydroxyarylethynylnaphthalene (4-18 g).
For this reaction, the above synthesis method (4-18c) can be referred to.

Further, (4-18 g) is reacted with a trifluoromethane sulfonating agent to obtain thioalkaryl arylethynyl naphthyl triflate (4-18 h).
For this reaction, the above synthesis method (4-18d) can be referred to.

Using (4-18d) and (4-18h) obtained as described above, a dinaphthylethylene derivative was prepared by coupling reaction with trans-1,2-bis (tributyltin) ethylene in the presence of a palladium catalyst. (4-18i) is obtained.
As the palladium catalyst and the reaction solvent, those described in the above synthesis method (4-2c) can be used.
This reaction proceeds with only the palladium catalyst, but a cocatalyst may be used to shorten the reaction time or improve the yield. Examples of the cocatalyst include metal halides such as lithium chloride, sodium chloride, and zinc chloride, and coordination compounds such as triphenylphosphine and triphenylarsine. These can be used alone or in combination of two or more. Also good. The amount of the cocatalyst used is not particularly limited as long as (4-18i) is obtained, and is, for example, 0.01 to 200 equivalents, preferably 0.1 to 20 equivalents with respect to the palladium catalyst. Moreover, the usage ratio of (4-18d), (4-18h) and bis (dibutyltin) ethylene is not particularly limited as long as the desired (4-18i) can be obtained. (4-18d) / (4-18h) / bis (dibutyltin) ethylene = 1 / 0.1 to 10 / 0.05 to 5.
The reaction temperature is not particularly limited as long as (4-18i) is obtained, and is, for example, -20 ° C to 300 ° C, preferably 0 ° C to 200 ° C.

Finally, (4-18i) is reacted with a halogenating agent, ring-closed, and alkylarylethynylnaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene (4-18) )

As the halogenating agent, those described in the above synthesis method (4-2a) can be used as they are.
Although this reaction proceeds without using a catalyst, a catalyst may be used to shorten the reaction time or improve the yield. As the catalyst, for example, copper catalysts such as copper iodide, copper bromide, copper chloride, copper acetate, copper trifluoroacetate, copper cyanide, copper trifluoromethanesulfonate, and the like can be used.
The said copper catalyst can be used individually or in combination of 2 or more types, The usage-amount will not be restrict | limited especially if (4-18) is obtained, For example, 0.001 with respect to a dinaphthyl ethylene derivative. -10 equivalents, preferably 0.01-1 equivalent.

The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, and dibutyl ether, and esters such as ethyl acetate, isopropyl acetate, and amyl acetate. Solvent, aliphatic hydrocarbon solvent such as n-hexane, heptane, octane, cyclohexane, cyclopentane, etc., ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, 1, 2 -Halogenated solvents such as dichloroethane, aromatic hydrocarbon solvents such as toluene, benzene and xylene; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrodinone; Kishido, sulfur-containing solvents such as sulfolane, acetonitrile, valeronitrile, nitrile solvents such as benzonitrile, acetic acid, propionic acid, and carboxylic acid solvents such as butyric acid.
The reaction temperature is not particularly limited as long as (4-18) is obtained, and is, for example, -20 ° C to 300 ° C, preferably 0 ° C to 200 ° C.

(Electronic structure)
From the viewpoint of applying the organic semiconductor material according to the present invention to a device, the energy levels of the HOMO and LUMO of the core part are also important. In general, the HOMO and LUMO levels of an organic semiconductor material provide a measure of electrical contact with the anode and cathode, respectively, and charge injection is limited by the size of the energy barrier determined by the difference from the work function of the electrode material. So be careful. The work function of a metal is often silver (Ag) 4.0 eV, aluminum (Al) 4.28 eV, gold (Au) 5.1 eV, calcium (Ca) 2.87 eV, as examples of materials used as electrodes. Chromium (Cr) 4.5 eV, copper (Cu) 4.65 eV, magnesium (Mg) 3.66 eV, molybdenum (Mo) 4.6 eV, platinum (Pt) 5.65 eV, indium tin oxide (ITO) 4. 35 to 4.75 eV and zinc oxide (ZnO) 4.68 eV, but from the above viewpoint, the work function difference between the organic semiconductor material and the electrode substance is preferably 1 eV or less, more preferably 0.8 eV or less. More preferably, it is 0.6 eV or less. As for the work function of the metal, the following documents can be referred to as necessary.
Document D: Chemical Handbook Fundamentals Revised 5th Edition II-608-610 14.1 b Work Function (Maruzen Publishing Co., Ltd.) (2004)

(Mobility)
The mobility when the compound of the present invention is used as an organic semiconductor material is the mobility of carriers such as holes and electrons, and serves as an index representing the semiconductor performance of the organic semiconductor material. The mobility includes mobility (μ ^TOF : unit cm ² / V · s) by a TOF (Time-of-Flight) method, and mobility (μ ^FET : unit cm ² / V · s) determined by a transistor. Yes, as μ ^TOF and ^{μ FET} is high, it will be easy carriers flow.
The mobility (μ ^TOF ) is obtained by the following formula (i), where V is the voltage between the electrodes of the TOF measurement cell, d is the distance between the electrodes, and Tr is the time crossing the film thickness calculated from the photocurrent waveform. It is done. The mobility (μ ^FET ) is obtained by the following equation (ii) using a transfer characteristic curve obtained by fixing the drain voltage V _d and changing the gate voltage V _sg . In the following, ^μFET may be simply expressed as μ.

(In formula (ii), C is the capacitance per unit area of the gate insulating film, I _d is the drain current, L is the channel length, W is the channel width, and _VT is the threshold voltage.)

(Organic semiconductor ink)
When the compound of the present invention is used as an organic semiconductor material, a semiconductor film may be formed by vacuum deposition, but it is preferably used as a printing ink that can be formed at a low temperature and has excellent productivity. In order to prepare the ink, the compound of the present invention is dissolved in a solvent, and in order not to impair the semiconductor performance, a leveling agent such as a fluorine-based or silicon-based material, polystyrene, acrylic resin, etc. These polymer compounds can also be added as a viscosity modifier.
Any organic solvent may be used, or two or more organic solvents may be mixed and used. Specifically, aliphatic solvents such as n-hexane, n-octane, n-decane and n-dodecane; alicyclic solvents such as cyclohexane; benzene, toluene, cumene, o-xylene, m-xylene, p-xylene, p-cymene, mesitylene, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,5-dimethylanisole, 3,5-dimethoxytoluene, 2,4-dimethylanisole, phenetole, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, 1,5-dimethyltetralin, n-propylbenzene, n-butylbenzene, n-pentylbenzene, 1,3,5-triethylbenzene, 1,3 -Dimethoxybenzene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, etc. Aromatic solvents: ether solvents such as tetrahydrofuran, dioxane, ethylene glycol diethyl ether, anisole, benzyl ethyl ether, ethyl phenyl ether, diphenyl ether, methyl-t-butyl ether; methyl acetate, ethyl acetate, ethyl cellosolve, propylene glycol methyl ether Ester solvents such as acetate; alcohol solvents such as methanol, ethanol, isopropanol; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-hexanone, 2-heptanone, 3-heptanone; other dimethylformamide, dimethylsulfoxide, diethylformamide However, it is not limited to these.

The concentration of the compound of the present invention in the prepared liquid composition is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.
One kind of organic solvent may be used, but a plurality of kinds of solvents may be mixed and used in order to obtain a desired thin film with high homogeneity.
In addition to the compound of the present invention, the organic semiconductor ink of the present invention includes other organic semiconductor materials, that is, electron donating materials, electron accepting materials, electron transporting materials, hole transporting materials, light emitting materials, light An absorbent material or the like may be included. Examples of such materials include π-conjugated polymers that exhibit semiconducting properties, non-π conjugated polymers that exhibit semiconducting properties, and low molecular organic semiconductor compounds.
The organic semiconductor ink of the present invention provides a homogeneous organic semiconductor film having a high order of molecular arrangement. Therefore, the obtained organic semiconductor film can exhibit high mobility. In addition, in order to obtain a highly ordered film with molecular arrangement, there is no need to perform special printing or special treatment such as thermal annealing. High mobility organic semiconductors can be obtained simply by dropping and drying the ink. A membrane is obtained.

(Organic semiconductor device)
Next, the organic semiconductor device of the present invention will be described. The organic semiconductor device of the present invention is an organic semiconductor device containing the compound of the present invention in an active layer portion (semiconductor layer). Specific examples of organic semiconductor devices include: diodes; memories; photoelectric conversion elements such as photodiodes, solar cells, and light receiving elements; transistors such as field effect transistors, electrostatic induction transistors, and bipolar transistors; electroluminescence elements (organic EL) light emitting element such as and light emission transistor; temperature sensor, a chemical sensor, a gas sensor, humidity sensor, radiation sensor, biosensor, blood sensor, immunization sensor, artificial retina, taste sensor, sensors such as pressure sensors; RFID such as a logic circuit Examples of the unit include, but are not limited to these.
Especially, since the organic-semiconductor material of this invention has a high charge mobility of 0.1 cm < ² > / Vs or more, the application to an organic transistor or a light emitting transistor is especially useful. The organic transistor can be suitably used as a switching transistor, a signal driver circuit element, a memory circuit element, a signal processing circuit element, or the like of a pixel constituting the display. Examples of the display include a liquid crystal display, a dispersive liquid crystal display, an electrophoretic display, a particle rotating display element, an electrochromic display, an organic electroluminescence display, and electronic paper.

(Organic transistor)
Next, the organic transistor containing the compound of the present invention will be described.
An organic transistor usually includes a source electrode, a drain electrode and a gate electrode, a gate insulating layer, and an organic semiconductor layer, and there are various types of transistors depending on the arrangement of each electrode and each layer. This compound is not limited to the type of transistor and can be used for any transistor. For the types of transistors, reference can be made to Aldrich Basic Material Science No. 6 “Basics of Organic Transistors”.

  As an example, FIG. 1 is a conceptual diagram of a top contact transistor (hereinafter referred to as a TC type), and FIG. 2 is a conceptual diagram of a bottom contact transistor (hereinafter referred to as a BC type). In the figure, 1 is a substrate, 2 is a gate electrode, 3 is a gate insulating layer, 4 is an organic semiconductor, 5 is a source electrode, and 6 is a drain electrode.

Here, the BC type is a semiconductor material that is inferior to other element forming materials (metals for electrode materials and resins for gate insulating materials) in terms of heat resistance, weather resistance and solvent resistance. Since it is handled, it is superior in wet process suitability (suitability for producing elements by printing, coating, etc.) and has a more practical structure. On the other hand, the BC type tends to be inferior to the device characteristics as compared to the TC type (Aldrich Basic Material Science No. 6 “Basics of Organic Transistors”, section 2.2).
The characteristic of the compound of the present invention is that the known and conventional semiconductor compounds show high characteristics in the TC type, but the characteristics are not reproduced in the BC type, but the BC type is equivalent to the TC type as described later. It is to show the characteristics. This is presumably because the compound of the present invention is self-organized in the vicinity of the electrode as described above, and the electrical contact between the electrode and the semiconductor film interface is optimized.

  For the substrate 1, silicon, glass, various resin materials, or the like can be used. Various resin materials include, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC). , Cellulose triacetate (TAC), cellulose acetate propionate (CAP), acrylic resin, and the like. By using such a resinous material, the weight can be reduced as compared with the case of using glass, the portability can be improved, and the resistance to impact can be improved.

The electrode material of the gate electrode, source electrode, or drain electrode is not particularly limited as long as it is a conductive material. For example, platinum, gold, silver, nickel, chromium, copper, iron, tin, tin oxide / antimony, oxidation Indium tin (ITO), fluorine-doped zinc oxide, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium , Sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium It can be cited metal material such as aluminum mixture. In addition, known conductive polymers whose conductivity has been improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, “complex of polyethylene dioxythiophene and polystyrene sulfonic acid” or the like are also preferably used.

  As a method for forming an electrode, the above materials are used as raw materials, such as a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, and an atmospheric pressure plasma method. Dry process, inkjet method, gravure printing method, gravure offset printing method, offset printing method, relief printing method, relief printing method, screen printing method, micro contact printing method, reverse coater method, air doctor coater method, blade coater method , Air knife coater method, roll coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, electrostatic coater method, ultrasonic spray coater method, die coater method, Pinkota method, a bar coater method, a slit coater method, include wet process drop casting, it may be appropriately used depending on the material. More specifically, a method for forming an electrode through a pattern mask or the like using a dry process such as vacuum deposition or sputtering, a conductive solid film formed by a dry process such as vacuum deposition or sputtering, and a conventional photolithographic method- A method of forming an electrode by an etching method, a method of forming an electrode by combining a dry process such as vacuum deposition or sputtering and a photolithographic method-lift-off method, a conductive solid film formed by using a dry process such as vacuum deposition or sputtering, For example, a method of etching using a resist by inkjet or the like may be used. Alternatively, the conductive fine particle dispersion or the conductive polymer solution or dispersion may be directly patterned by a wet process such as an ink jet method, a screen printing method, a gravure offset printing method, a letterpress reverse printing method, or a micro contact printing method. Then, after forming a solid film by coating film formation, patterning may be performed by a combination of a known and commonly used photolithographic method-etching method, a laser ablation method, or the like, or a wet process and a photolithographic method-lift-off method. Patterning may be performed in combination.

  Gate insulating layer is a thermoplastic resin such as parylene, polystyrene, acrylic resin, polyester resin; thermosetting resin such as epoxy resin, urethane resin, phenol resin, unsaturated polyester resin, alkyd resin, melamine resin; UV curable resin An organic thin film such as a silicon oxide film can be suitably used, but inorganic materials such as a silicon oxide film can also be used.

  The gate insulating layer is formed by a spin coating method, a casting method, a dipping method, an ink jet method, a doctor blade method, a screen printing method, an offset printing method, a letterpress printing method, a reverse printing method, a micro contact printing method, a wire bar coating method, a spray coating method. A thin film can be prepared by a known wet film forming method such as a dispensing method, and may be patterned into a necessary shape by a photolithographic method, if necessary.

The organic semiconductor layer can be produced by a known and common production method such as a vacuum vapor deposition method, but the organic semiconductor layer can be easily formed by a printing method using an organic semiconductor ink as a material.
Examples of printing methods include inkjet method, gravure printing method, gravure offset printing method, offset printing method, relief printing method, relief printing method, screen printing method, micro contact printing method, reverse coater method, air doctor coater method , Blade coater method, air knife coater method, roll coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, electrostatic coater method, ultrasonic spray coater method, die coater It is possible to produce a thin film by a known wet film forming method such as a method, a spin coater method, a bar coater method, a slit coater method, a drop cast method, or a dispense method. Further, depending on the casting method or the like, it is possible to take a form of a flat crystal or a thick film state.
The organic transistor of the present invention can be suitably used as a switching transistor, a signal driver circuit element, a memory circuit element, a signal processing circuit element or the like of a pixel constituting a display. Examples of the display include a liquid crystal display, a dispersed liquid crystal display, an electrophoretic display, a particle rotating display element, an electrochromic display, an organic electroluminescence display, and electronic paper.

  The present invention will be described in more detail with reference to synthesis examples and examples.

Synthesis Example 1 Synthesis of Compound (IV-3) in Chemical Formula 26

Acetic acid (350 mL) was added to 1,5-dihydroquinaphthalene (10.0 g, 62.4 mmol) and iodine (130 mg), and the mixture was stirred at room temperature. The reaction solution was heated to 80 ° C., and a solution of 6.5 mL (127 mmol) of bromine in 28 mL of acetic acid was slowly added dropwise. After stirring at 80 ° C. for 5 minutes, the reaction solution was air-cooled to room temperature. The precipitated green needle crystal was collected by filtration. The obtained solid was recrystallized from 200 mL of acetic acid to obtain 11.8 g (yield, 62.1%) of 2,6-dibromo-1,5-dihydroxynaphthalene.

Add 90 mL of dichloromethane to 3.09 g (9.72 mmol) of 2,6-dibromo-1,5-dihydroquinaphthalene and 0.68 g (5.57 mmol) of 4- (N, N-dimethyl) aminopyridine, and stir at room temperature. did. The suspension was ice-cooled, and 3.3 mL (2.13 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise at 5 ° C. or lower. After stirring for 2.5 hours under ice-cooling, the reaction was stopped by adding 60 mL of water and 10 mL of 1M hydrochloric acid, followed by extraction with dichloromethane. The crude product obtained by concentrating the organic phase was separated and purified by silica gel column chromatography (chloroform) to obtain 3.97 g of 2,6-dibromo-1,5-bis (trifluoromethylsulfonyloxy) naphthalene (yield) 70.1%).

Under an argon atmosphere, 1.82 g (9.60 mmol) of copper iodide, 3.37 g (4.80 mmol) of dichlorobistriphenylphosphine palladium (II), 2,6-dibromo-1,5-bis (trifluoromethylsulfonyloxy) ) 340 mL of N, N-dimethylformamide and 340 mL of diisopropylamine were added to 28.0 g (48.1 mmol) of naphthalene, and the mixture was stirred at room temperature. To the reaction solution, 13.8 mL (48.1 mmol) of trimethylsilylacetylene was added. After stirring at room temperature for 16 hours, the reaction solution was poured into a mixture of 3 L of water and 50 mL of 1M hydrochloric acid, and the resulting solid was collected by filtration and dried. The obtained brown powder was separated and purified by silica gel column chromatography (hexane) to obtain 16.3 g (yield, 71.0%) of 2,6-dibromo-1,5-bis (trimethylsilylethynyl) naphthalene. It was.

Under an argon atmosphere, 776 mL of N-methylpyrrolidinone was added to 26.6 g (111 mmol) of sodium sulfide nonahydrate, and the mixture was stirred for 15 minutes. To the reaction solution, 15.0 g (25.8 mmol) of 2,6-dibromo-1,5-bis (trimethylsilylethynyl) naphthalene was added and heated to reflux for 7 hours. After air cooling to room temperature, the reaction solution was poured into 2.5 L of a saturated aqueous ammonium chloride solution, and the resulting solid was collected by filtration and dried. The obtained yellow powder was dispersed in chloroform, and the soluble component was collected by filtration and concentrated. The obtained yellow powder was separated and purified by silica gel column chromatography (chloroform) to obtain 3.40 g (yield, 54.9%) of naphtho [2,1-b: 6,5-b ′] dithiophene. It was.

Under an argon atmosphere, 250 mL of tetrahydrofuran was added to 2.10 g of naphtho [2,1-b: 6,5-b ′] dithiophene (8.74 mmol) and cooled to −78 ° C. To the reaction solution, 6.7 mL (11 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction solution was warmed to 0 ° C. and further stirred for 2 hours. After dropwise addition of 2.2 mL (11 mmol) of n-decyl bromide at 0 ° C., the mixture was warmed to room temperature and stirred for 18 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (hexane / chloroform = 95/5) to give 0.961 g of 2-decylnaphtho [2,1-b: 6,5-b ′] dithiophene (yield, 28.9%).

Under an argon atmosphere, 50 mL of tetrahydrofuran was added to 0.895 g (2.35 mmol) of 2-decylnaphtho [2,1-b: 6,5-b ′] dithiophene and cooled to −78 ° C. To the reaction solution, 2.5 mL (3.58 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional 2.5 hours. The reaction solution was cooled to -78 ° C, and a solution of 0.658 g (2.59 mmol) of iodine in 16 mL of tetrahydrofuran was slowly added dropwise, and then the mixture was warmed to room temperature and stirred for 16 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (hexane) to give 0.550 g of 2-decyl-7-iodonaphtho [2,1-b: 6,5-b ′] dithiophene (yield, 46. 2%).

Under an argon atmosphere, 0.0039 g (0.021 mmol) of copper iodide, 0.0011 g (0.00093 mmol) of tetrakis (triphenylphosphine) palladium (0), 2-decyl-7-iodonaphtho [2,1-b: 6 , 5-b ′] dithiophene 0.104 (0.205 mmol) was added tetrahydrofuran 0.4 mL and triethylamine 0.2 mL and stirred at room temperature. A solution of 0.0391 g (0.383 mmol) of ethynylbenzene in 0.2 mL of tetrahydrofuran was added to the reaction solution, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 30 mL of water, the resulting precipitate was filtered, and the resulting solid was washed with methanol, dissolved in chloroform and concentrated. The obtained crude product was separated by silica gel column chromatography (hexane). The obtained crude product was recrystallized from acetone to give 2-decyl-7- (phenylethynyl) naphtho [2,1-b: 6,5-b ′] dithiophene represented by (III-2). 113 g (yield, 46.5%) were obtained.
¹ H NMR (300 MHz, CDCl ₃ ): δ 8.244 (d, J = 8.7 Hz, 1H), δ 8.182 (s, 1H), δ 8.146 (d, J = 8.7 Hz, 1H), δ7 .941 (d, J = 8.7 Hz, 1H), δ7.891 (d, J = 8.7 Hz, 1H), δ7.681 (s, 1H), δ7.577-7.606 (m, 2H) , Δ 7.377-7.428 (m, 3H), δ 3.025 (t, J = 7.2 Hz, 2H), δ 1.77-1.875 (m, 2H), δ 1.386-1.512 ( m, 14H), δ 0.878 (t, J = 5.7 Hz, 3H).
FD-MS: [M] ⁺ = 480.3

Synthesis Example 2 Synthesis of Compound (IV-2) in Chemical Formula 26

300 mL of dichloromethane was added to 3.18 g (10.0 mmol) of 2,6-dibromo-1,5-dihydroquinaphthalene, and the mixture was stirred at room temperature. To the reaction solution, 2.0 mL (24.8 mmol) of pyridine and 5.0 mL (30.5 mmol) of acetic anhydride were slowly added dropwise and heated to reflux for 1 hour. After air cooling to room temperature, 30 mL of 1N hydrochloric acid was added to stop the reaction. The reaction solution was extracted with dichloromethane, dried over magnesium sulfate and concentrated to dryness. The obtained crude product was washed with methanol to obtain 3.97 g (yield, 98.7%) of 2,6-dibromo-1,5-diacetoxynaphthalene.

Under argon atmosphere, CuI 0.0568 g (0.30 mmol), dichlorobis (benzonitrile) palladium (II) 0.172 g (0.45 mmol), 2,6-dibromo-1,5-diacetoxynaphthalene 2.96 g (7. 31 mmol) was added with 7.5 mL of tetrahydrofuran and 2.5 mL of diisopropylamine, and stirred at room temperature. To the reaction solution, 2.2 mL (17.9 mmol) of trimethylsilylacetylene was added. After stirring at room temperature for 17 hours, the resulting solid was collected by filtration and the filtrate was dried. The resulting brown powder was separated and purified by silica gel column chromatography (hexane / chloroform = 30/70) to obtain 1.36 g of 2,6-bis (trimethylsilylethynyl) -1,5-diacetoxynaphthalene (yield, 43%). )

Under an argon atmosphere, 109 mL of tetrahydrofuran was added to 8.76 mL (8.76 mmol) of a 1.0 mol / L tetrahydrofuran solution of n-tetrabutylammonium fluoride and 2.16 g of Molecular Sieves 4A, and the mixture was stirred at room temperature for 1 hour. To the reaction solution was added 36 mL of a tetrahydrofuran solution of 1.20 g (2.75 mmol) of 2,6-bis (trimethylsilylethynyl) -1,5-diacetoxynaphthalene, and the mixture was stirred for 15 hours under heating to reflux. After cooling to room temperature, the reaction solution was filtered. The filtrate was washed with saturated brine, dried over magnesium sulfate and concentrated to dryness. The obtained crude product was separated and purified by silica gel column chromatography (chloroform) to obtain 0.33 g (yield, 58%) of naphtho [1,2-b: 5,6-b ′] difuran.

Under argon atmosphere, naphtho [1,2-b: 5,6-b ′] difuran 2.90 g, (13.9 mmol), N, N, N ′, N′-tetramethylethylenediamine to 2.3 mL (16 mmol) Tetrahydrofuran 100mL was added and it cooled at -78 degreeC. To the reaction solution, 4.8 mL (7.6 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional 2 hours. After dropwise addition of 1.6 mL (7.54 mmol) of n-decyl bromide at room temperature, the mixture was warmed to room temperature and stirred for 18 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (hexane) to obtain 1.18 g (yield, 24%) of 2-decylnaphtho [1,2-b: 5,6-b ′] difuran. .

Under an argon atmosphere, 30 mL of chloroform and 30 mL of acetic acid were added to 0.70 g (2.00 mmol) of 2-decylnaphtho [1,2-b: 5,6-b ′] difuran and cooled to 0 ° C. To the reaction solution, 0.49 g (2.2 mmol) of N-iodosuccinimide was added little by little. The reaction was warmed to room temperature and stirred overnight. The solvent was distilled off, and the resulting crude product was separated and purified by silica gel column chromatography (hexane) to give 0.24 g of 2-decyl-7-iodonaphtho [1,2-b: 5,6-b ′] difuran. 0.28 g (yield, 25%) was obtained (2.00 mmol).

Under an argon atmosphere, 0.0056 g (0.029 mmol) of copper iodide, 0.017 g (0.0017 mmol) of tetrakis (triphenylphosphine) palladium (0), 2-decyl-7-iodonaphtho [1,2-b: 5 , 6-b ′] difuran (0.65 mL) and triethylamine (0.2 mL) were added to 0.15 g (0.32 mmol) and stirred at room temperature. To the reaction solution was added a solution of 0.046 g (0.45 mmol) of ethynylbenzene in 0.2 mL of tetrahydrofuran, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into 30 mL of water, the resulting precipitate was filtered, and the resulting solid was washed with methanol, dissolved in chloroform and concentrated. The obtained crude product was separated and purified by silica gel column chromatography (hexane) to give 0.11 g of 2-decyl-7- (phenylethynyl) naphtho [1,2-b: 5,6-b ′] difuran (yield). Rate, 75%).
¹ H NMR (300 MHz, CDCl ₃ ): δ 8.16-8.12 (m, 2H), δ 7.70 (dd, J = 8.4 Hz, J = 3.3 Hz, 2H), δ 7.61-7. 63 (m, 2H), δ 7.40 (m, 3H), δ 7.26 (s, 1H), δ 6.55 (s, 1H), δ 2.88 (t, J = 7.2 Hz, 2H), δ1 .76-1.88 (m, 2H), δ 1.19-1.51 (m, 14H), δ 0.86 (t, J = 6.9 Hz, 3H).
FD-MS: [M] ⁺ = 448.2

Synthesis Example 3 Synthesis of Compound (IV-1) in Chemical Formula 26

To 3.0 g (16 mmol) of 2,6-dimethoxynaphthalene, 150 mL of chloroform and 150 mL of acetic acid were added and stirred at room temperature. To the reaction solution, 6.2 g (35 mmol) of N-bromosuccinimide was added. After 5 hours of stirring at room temperature, the reaction solution was filtered. The obtained solid was washed with water, a saturated aqueous sodium hydrogen carbonate solution and ethanol in this order to obtain 4.8 g of 1,5-dibromo-2,6-dimethoxynaphthalene (yield, 87%).

750 mL of dichloromethane was added to 17.3 g (50 mmol) of 1,5-dibromo-2,6-dimethoxynaphthalene, and the mixture was stirred at 0 ° C. To the reaction solution, 174 mL (174 mmol) of a boron tribromide 1.0 mol / L dichloromethane solution was slowly added dropwise. After stirring for 30 minutes at room temperature, the reaction solution was filtered. The obtained solid was washed with water to obtain 14.9 g of 1,5-dibromo-2,6-dihydroxynaphthalene (yield, 94%).

1,400 mL of dichloromethane was added to 14.9 g (47 mmol) of 1,5-dibromo-2,6-dihydroxynaphthalene and 9,0 mL (111 mmol) of pyridine, followed by stirring at room temperature. To the reaction solution, 23.3 mL (187 mmol) of acetic anhydride was added. After stirring for 4 hours at room temperature, 10 mL of 1N hydrochloric acid was added to stop the reaction, and then the organic phase and the aqueous phase were separated. The aqueous phase was further extracted with dichloromethane, the organic phases were combined, dried over magnesium sulfate and concentrated to dryness. The obtained crude product was crystallized from cyclohexane to obtain 17.0 g (yield, 90%) of 1,5-dibromo-2,6-diacetoxynaphthalene.

Under an argon atmosphere, 11.8 g (29.3 mmol) of 1,5-dibromo-2,6-diacetoxynaphthalene, 25.2 mL (67.5 mmol) of tributyl (trimethylsilylethynyl) tin, dichlorobis (triphenylphosphine) palladium (II 200 mL of toluene was added to 2.06 g (2.94 mmol) and stirred at room temperature. After 7 hours of stirring under heating and reflux, the mixture was cooled to room temperature. The reaction was stopped by adding 100 mL of 1N hydrochloric acid, and then separated into an organic phase and an aqueous phase. The aqueous phase was further extracted with dichloromethane, the organic phases were combined, dried over magnesium sulfate and concentrated to dryness. The obtained crude product was crystallized from cyclohexane to obtain 10.2 g (yield, 80%) of 1,5-dibromo-2,6-bis (trimethylethynyl) naphthalene.

Under an argon atmosphere, 190 mL of tetrahydrofuran was added to 51.3 mL (51.3 mmol) of a 1.0 mol / L tetrahydrofuran solution of n-tetrabutylammonium fluoride and 4.3 g of Molecular Sieves 4A, and the mixture was stirred at room temperature for 1 hour. To the reaction solution was added 42 mL of a tetrahydrofuran solution of 3.0 g (6.87 mmol) of 1,5-dibromo-2,6-bis (trimethylethynyl) naphthalene, and the mixture was stirred for 5 hours under heating to reflux. After cooling to room temperature, the reaction solution was filtered. The filtrate was washed with saturated brine, dried over magnesium sulfate and concentrated to dryness. The obtained crude product was separated and purified by silica gel column chromatography (hexane) to obtain 0.75 g of naphtho [2,1-b: 6,5-b ′] difuran (yield, 70% was obtained).

Under argon atmosphere, 12 mL of tetrahydrofuran was added to 0.30 g of naphtho [2,1-b: 6,5-b ′] difuran (1.44 mmol) and cooled to −78 ° C. To the reaction solution, 1.0 mL (1.6 mmol) of a 1.6 mol / L hexane solution of n-butyllithium was slowly added dropwise. The reaction was warmed to room temperature and stirred for an additional 2 hours. After dropwise addition of 1.5 mL (7.3 mmol) of n-decyl bromide at 0 ° C., the mixture was warmed to room temperature and stirred for 4 hours. Water was added to the reaction solution to stop the reaction, and then the solvent was distilled off. The obtained crude product was separated and purified by silica gel column chromatography (cyclohexane / ethyl acetate = 97/3) to give 0.151 g of 2-decylnaphtho [2,1-b: 6,5-b ′] difuran ( Yield, 30.1%).

  Under an argon atmosphere, 30 mL of chloroform and 30 mL of acetic acid were added to 0.70 g (2.00 mmol) of 2-decylnaphtho [2,1-b: 6,5-b ′] difuran and cooled to 0 ° C. To the reaction solution, 0.50 g (2.2 mmol) of N-iodosuccinimide was added little by little. The reaction was warmed to room temperature and stirred overnight. The solvent was distilled off, and the resulting crude product was separated and purified by silica gel column chromatography (hexane) to give 0.28 g of 2-decyl-7-iodonaphtho [2,1-b: 6,5-b ′] difuran. (Yield, 30%) was obtained.

Under an argon atmosphere, 0.008 g (0.04 mmol) of copper iodide, 0.023 g (0.02 mmol) of tetrakis (triphenylphosphine) palladium (0), 2-decyl-7-iodonaphtho [2,1-b: 6 , 5-b ′] difuran 0.20 g (0.40 mmol) was added 1 mL of tetrahydrofuran and 0.5 mL of triethylamine, and the mixture was stirred at room temperature. Ethinylbenzene 0.082g (0.80mmol) was added to the reaction liquid, and it stirred at room temperature for 30 minutes. The reaction mixture was poured into 50 mL of water, the resulting precipitate was filtered, and the resulting solid was washed with methanol, dissolved in chloroform and concentrated. The obtained crude product was separated by silica gel column chromatography (hexane). The obtained crude product was recrystallized from acetone to obtain 0.095 g of 2-decyl-7- (phenylethynyl) naphtho [2,1-b: 6,5-b ′] difuran (yield, 50 .5%).
¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ 7.98 (d, J = 9.0 Hz, 1H), δ 7.87 (d, J = 8.7 Hz, 1H), δ 7.65 (dd, J = 5.7 Hz, J = 0.9 Hz, 1H), δ 7.62 (dd, J = 5.4 Hz, J = 0.6 Hz, 1H), δ 7.51-7.58 (m, 2H), δ 7.48. (D, J = 0.9 Hz, 1H), δ 7.31-7.39 (m, 3H), δ 6.86 (d, J = 0.6 Hz, 1H), δ 2.81 (t, J = 7. 5Hz, 2H), δ 1.70-1.80 (m, 2H), δ 1.15-1.55 (m, 14H), δ 0.80 (t, J = 6.6 Hz, 3H) ppm.
FD-MS: [M] ⁺ = 448.2

Synthesis Example 4 Synthesis of Compound (IV-18) in Chemical Formula 27

Under argon atmosphere, 5.0 g (21 mmol) of 6-bromo-2-methoxynaphthalene and 0.57 g (1.1 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) were dissolved in 21 mL of tetrahydrofuran. The mixture was stirred while cooling in an ice bath, and 23 mL (23 mmol) of a 1.0 mol / L diethyl ether solution of n-decylmagnesium bromide was slowly added dropwise. The reaction solution was stirred under reflux for 4 hours, and then 20 mL of water was slowly added dropwise in an ice bath. This reaction solution was extracted three times with 100 mL of diethyl ether, and the extract was washed three times with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude liquid. This liquid was separated and purified by silica gel column chromatography (ethyl acetate / hexane = 5/95) to obtain 4.5 g (yield 71%) of 6-decyl-2-methoxynaphthalene as a pale yellow transparent liquid.

  Under an argon atmosphere, 4.0 g (13 mmol) of 6-decyl-2-methoxynaphthalene was dissolved in 50 mL of tetrahydrofuran, cooled to −70 ° C. or lower with stirring, and a 1.6 mol / L hexane solution of n-butyllithium 9 After 2 mL (15 mmol) was added dropwise, the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was again cooled to −70 ° C. or lower, and 1.6 g (17 mmol) of dimethyl disulfide was added dropwise, followed by stirring at room temperature for 1.5 hours. Thereafter, 50 mL of a saturated aqueous ammonium chloride solution was added, extracted three times with diethyl ether, washed three times with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude liquid. The crude liquid was separated and purified by silica gel column chromatography (toluene) to obtain 5.4 g (100%) of 6-decyl-2-methoxy-3-methylthionaphthalene as a pale yellow transparent liquid.

Under an argon atmosphere, 4.2 g (12 mmol) of 6-decyl-2-methoxy-3-methylthionaphthalene was dissolved in 100 mL of dichloromethane, cooled to −70 ° C. or lower with stirring, and 1.0 mol / mol of boron tribromide. After dropwise addition of 23 mL (23 mmol) of L dichloromethane solution, the mixture was warmed to room temperature and stirred for 3 hours. Thereafter, 60 g of ice was added in an ice bath and stirred for 15 minutes. This reaction solution was extracted 3 times with 50 mL of dichloromethane, washed 3 times with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude solid. This crude solid was separated and purified by silica gel column chromatography (cyclohexane / chloroform = 50/50) to obtain 3.3 g (yield 82%) of 6-decyl-3-methylthio-2-naphthol as a white solid.

Under argon atmosphere, 3.1 g (9.4 mmol) of 6-decyl-3-methylthio-2-naphthol was dissolved in 22 m of dichloromethane, 2.3 mL (29 mmol) of pyridine was added, and the mixture was cooled to about 0 ° C. with stirring. After dropwise addition of 3.0 g (11 mmol) of trifluoromethanesulfonic anhydride, the mixture was warmed to room temperature and stirred for 4 hours. To this reaction solution, 30 mL of 2N hydrochloric acid was added, stirred, extracted three times with 20 mL of dichloromethane, washed three times with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude solid. . This crude solid was separated and purified by silica gel column chromatography (cyclohexane / toluene = 80/20) to obtain 3.1 g (yield 71%) of 6-decyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene as a white solid. Obtained.

6-bromo-2-methoxynaphthalene 10 g (42 mmol), copper iodide 0.16 g (0.84 mmol), dichlorobis (benzonitrile) palladium (II) 0.51 g (1.3 mmol), diisopropylamine 8.5 g (84 mmol) And nitrogen gas was bubbled for 15 minutes at room temperature. 1.68 mL (2.53 mmol) of a 1.5 mol / L toluene solution of tri-t-butylphosphine was added under a nitrogen atmosphere, 5.17 g (50.6 mmol) of ethynylbenzene was added, and the temperature was raised to 50 degrees. The mixture was heated and stirred for 8 hours. After cooling to room temperature, the reaction solution was added to 500 mL of water. Further, the produced solid was washed with 100 mL of acetone. After dissolving the solid in 150 mL of dichloromethane, 30 g of a metal scavenger was added to prepare a slurry. The slurry was removed by filtration, and the filtrate was dried over anhydrous magnesium sulfate and then concentrated to dryness to obtain a crude solid. The crude solid was recrystallized from cyclohexane to obtain 7.0 g (yield 65%) of 2-methoxy-6- (phenylethynyl) naphthalene as white crystals.

Under an argon atmosphere, 7.0 g (27 mmol) of 2-methoxy-6- (phenylethynyl) naphthalene was dissolved in 50 mL of tetrahydrofuran, cooled to −70 ° C. or lower with stirring, and 1.6 mol / L of n-butyllithium. After dropwise addition of 18 mL (29 mmol) of hexane solution, the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was again cooled to −70 ° C. or less, and 3.10 g (32.9 mmol) of dimethyl disulfide was added dropwise, followed by stirring at room temperature for 1.5 hours. Thereafter, 50 mL of a saturated aqueous ammonium chloride solution was added, extracted three times with diethyl ether, washed three times with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude solid. This crude solid was recrystallized from acetone / cyclohexane to obtain 4.5 g (55%) of 2-methoxy-3-methylthio-6- (phenylethynyl) naphthalene as white crystals.

Under an argon atmosphere, 3.0 g (9.8 mmol) of 2-methoxy-3-methylthio-6- (phenylethynyl) naphthalene obtained above was dissolved in 70 mL of dichloromethane and cooled to −70 ° C. or lower while stirring. After dropwise addition of 10.4 mL (10.4 mmol) of boron tribromide in 1 mol / L dichloromethane, the mixture was warmed to room temperature and stirred for 4 hours. Thereafter, 40 g of ice was added in an ice bath and stirred for 5 minutes. This reaction solution was extracted three times with 70 mL of dichloromethane, washed three times with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude solid. This crude solid was separated and purified by silica gel column chromatography (toluene) to obtain 1.5 g (yield 52%) of 3-methylthio-6- (phenylethynyl) -2-naphthol as a white solid.

3-methylthio-6- (phenylethynyl) -2-naphthol (1.4 g, 4.8 mmol) is dissolved in dichloromethane (12 mL), pyridine (1.3 mL, 16 mmol) is added, and the mixture is stirred at about 0 ° C. under an argon atmosphere with stirring. After cooling to 1.66 g (5.88 mmol) of trifluoromethanesulfonic anhydride, the mixture was warmed to room temperature and stirred for 4 hours. To this reaction solution, 30 mL of 2N aqueous hydrochloric acid was added, stirred, extracted three times with 20 mL of dichloromethane, washed three times with 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude solid. . This crude solid was separated and purified by silica gel column chromatography (cyclohexane / chloroform = 90 / 10-80 / 20) to give 3-methylthio-6- (phenylethynyl) -2-trifluoromethanesulfonyloxy-2-naphthol as a white solid. 0.87 g (42% yield) was obtained.

0.70 g (1.7 mmol) of 3-methylthio-6- (phenylethynyl) -2-trifluoromethanesulfonyloxynaphthalene and 0.77 g (1.7 mmol) of 6-decyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene Was dissolved in 13.3 mL of N, N-dimethylformamide, and nitrogen gas was bubbled while stirring at room temperature to produce 0.057 g (0.05 mmol) of tetrakis (triphenylphosphine) palladium (0), trans-1,2 -Bis (tributyltin) ethylene 1.00g (1.66mmol) was added, and it stirred at 100 degreeC for 46 hours in nitrogen atmosphere. 70 mL of water was added to the reaction solution, extracted three times with 50 mL of chloroform, washed three times with 100 mL of saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain a solid. This solid was dissolved in 150 mL of chloroform, and 30 g of a metal scavenger was added to prepare a slurry. The slurry was removed by filtration, and the filtrate was dried over anhydrous magnesium sulfate and then concentrated to dryness to obtain a crude solid. This crude solid was separated and purified by silica gel column chromatography (cyclohexane / chloroform = 90 / 10-80 / 20), and trans-1- [6- (phenylethynyl) -3-methylthionaphthalen-2-yl] as a white solid 0.16 g (20% yield) of 2- (6-decyl-3-methylthionaphthalen-2-yl) ethylene was obtained.

trans-1- (6- (phenylethynyl) -3-methylthionaphthalen-2-yl) -2- (6-decyl-3-methylthionaphthalen-2-yl) ethylene (0.1 g, 0.16 mmol) in chloroform / It melt | dissolved in 5 mL of mixed solvents of acetic acid = 50/50, 1.24 g (4.89 mmol) of iodine was added, stirring under argon atmosphere, and it stirred under recirculation | reflux for 56 hours. To this reaction liquid, 10 mL of chloroform was added, washed with 30 mL of a saturated aqueous sodium thiosulfate solution three times, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain a solid. The solid was purified by sublimation at 240 ° C. (vacuum degree: 10 ⁻³ Pa) to give 2- (phenylethynyl) -9-decyldinaphtho [2,3-b: 2 ′, 3′-f as a white solid. ] 24 mg (yield 25%) of thieno [3,2-b] thiophene was obtained.
FD-MS: 580.2

Synthesis Example 5 Synthesis of Compound (IV-17) in Chemical Formula 27

  Under argon atmosphere, 12 g (67 mmol) of 7-methoxy-2-naphthol was dissolved in 500 mL of dichloromethane, cooled to 0 ° C., and then stirred with 7.4 mL (94 mmol) of pyridine and 14 (81 mmol) of trifluoromethanesulfonic anhydride. It was dripped. After further stirring at 0 ° C. for 1.5 hours, a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. The lower layer was separated by separation, washed with saturated brine, and concentrated to dryness to obtain a crude liquid. This liquid was purified by silica gel column chromatography (dichloromethane) to obtain 20.5 g (yield, 100%) of 7-methoxy-2-trifluoromethanesulfonyloxynaphthalene.

Under argon atmosphere, 3.3 g (11 mmol) of 7-methoxy-2-trifluoromethanesulfonyloxynaphthalene 0.041 g (0.22 mmol) of copper iodide, 0.40 g (0.54 mmol) of dichlorobis (triphenylphosphine) palladium (II) ), 70 mL of tetrahydrofuran was added to 4.5 mL (32 mmol) of triethylamine, and after bubbling nitrogen gas for 10 minutes, the atmosphere was replaced with an argon atmosphere, and 4.3 mL (22 mmol) of 1-decyne was added dropwise. After stirring at room temperature for 5 hours, the mixture was diluted with dichloromethane, washed successively with water, 2M hydrochloric acid and saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness to give a crude liquid. This liquid was purified by silica gel column chromatography (dichloromethane) to give 2-methoxy-7- (decyn-1-yl) naphthalene. To this, 50 mL of tetrahydrofuran and 0.62 g of palladium carbon (10%) were added, nitrogen gas was bubbled for 10 minutes, and the atmosphere was replaced with a hydrogen atmosphere. After stirring at room temperature for 85 hours, the reaction solution was filtered and concentrated to dryness to obtain a crude liquid. This liquid was purified by silica gel column chromatography (dichloromethane) to obtain 3.2 g (yield, 100%) of 2-methoxy-7-decylnaphthalene.

Under argon atmosphere, 7.0 g (24 mmol) of 2-methoxy-7-decylnaphthalene was dissolved in 97 mL of tetrahydrofuran, cooled to −70 ° C., and stirred with 18 mL (28 mmol) of 1.6 mol / L hexane solution of n-butyllithium. ) Was added dropwise over 15 minutes. After stirring at 0 ° C. for 2 hours, 9.0 g (35 mmol) of iodine dissolved in 97 mL of tetrahydrofuran was added after cooling to −40 ° C. or lower. After returning to room temperature and stirring for 2 hours, an aqueous sodium thiosulfate solution was added to stop the reaction. The organic layer was taken, concentrated to dryness, dichloromethane was added, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness to give a crude liquid. This liquid was separated and purified by silica gel column chromatography (cyclohexane / dichloromethane = 30/70) to obtain 7.6 g of 6-decyl-2-iodo-3methoxynaphthalene (yield, 76%).

To 3.3 g (11 mmol) of 7-methoxy-2-trifluoromethanesulfonyloxynaphthalene, 0.041 g (0.22 mmol) of copper iodide, 0.40 g (0.54 mmol) of dichlorobis (triphenylphosphine) palladium (II), Triethylamine (4.5 mL, 32 mmol) and tetrahydrofuran (70 mL) were added under an argon atmosphere, and nitrogen gas was bubbled for 10 minutes. Then, the atmosphere was replaced with an argon atmosphere, and ethynylbenzene (1.3 mL, 12 mmol) was added dropwise. After stirring at room temperature for 5 hours, the mixture was diluted with dichloromethane, washed successively with water, 2M hydrochloric acid and saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness to give a crude solid. This solid was recrystallized from cyclohexane to obtain 1.6 g (yield, 58%) of 2-methoxy-7- (phenylethynyl) naphthalene.

  In an argon atmosphere, 5.4 g (23 mmol) of 2-methoxy-7- (phenylethynyl) naphthalene) was dissolved in 180 mL of tetrahydrofuran, cooled to −70 ° C., and stirred with 1.6 mol / L hexane of n-butyllithium. 17 mL (27 mmol) of the solution was slowly added dropwise. After stirring at 0 ° C for 2 hours, the mixture was cooled to -40 ° C or lower, and 5.7 mL (27 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added thereto. . After returning to room temperature and stirring for 1.5 hours, the mixture was diluted with dichloromethane, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, concentrated to dryness, and 3-methoxy-6- (phenylethynyl) naphthalene- 8.8 g (yield, 100%) of 2-ylboronic acid pinacol was obtained.

6-decyl-2-iodo-3methoxynaphthalene 6.0 g (14 mmol), 3-methoxy-6-phenylethynylnaphthalen-2-ylboronic acid pinacol 4.3 g (14 mmol), tetrakis (triphenylphosphine) palladium (0) 0.64 g (0.7 mmol) was dissolved in 85 mL of tetrahydrofuran under an argon atmosphere and stirred at room temperature. Thereto was added 42 mL of an aqueous solution in which 7.8 g (56 mmol) of potassium carbonate was dissolved, and the mixture was heated to reflux for 48 hours. After returning to room temperature, the organic layer was concentrated, diluted with dichloromethane, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness. The solid was purified by silica gel column chromatography (cyclohexane / dichloromethane = 90/10) to give 5.2 g of 2,2 ′-(6-phenylethynyl-6′-decyl-3,3′-dimethoxy) -binaphthalene (yield). Rate, 66%).

  Under an argon atmosphere, 3.0 g (3.7 mmol) of 6-decyl-3,3′-dimethoxy-6 ′-(phenylethynyl) -2,2′-binaphthalene was dissolved in 40 mL of dichloromethane, and then cooled to −70 ° C. While stirring, 6.9 mL (19 mmol) of a 1.6 mol / L dichloromethane solution of boron tribromide was added dropwise over 10 minutes. After heating to room temperature over 1 hour, it stirred for 1 hour. The reaction solution was washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness to give 6-decyl-3,3′-dihydroxy-6 ′-(phenylethynyl) -2,2′-. 2.9 g of binaphthalene (yield, 100%) was obtained.

Under an argon atmosphere, 1.0 g (1.9 mmol) of 6-decyl-3,3′-dihydroxy-6 ′-(phenylethynyl) -2,2′-binaphthalene was dissolved in 8 mL of tetrahydrofuran, and then 0.3 mL of triethylamine (2 0.0 mmol), 4- (N, N-dimethyl) aminopyridine (0.2 g, 1.9 mmol) and N, N-dimethylthiocarbamoyl chloride (0.9 g, 7.6 mmol) were added, and the mixture was heated to reflux for 24 hours. After returning to room temperature, the organic layer was concentrated, diluted with dichloromethane, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness. The solid was purified by silica gel column chromatography (cyclohexane / dichloromethane = 70/30) to give O, O′-6-decyl-3,3′-bis (N, N-dimethylthiocarbamoyl) -6 ′-( Phenylethynyl) -2,2′-binaphthalene-3,3′-diylbis (N, N-dimethylthiocarbamate) 0.8 g (yield, 60%) was obtained.

O, O′-6-decyl-3,3′-bis (N, N-dimethylthiocarbamoyl) -6 ′-(phenylethynyl) -2,2′-binaphthalene-3,3′-diylbis (N, 1.0 g (1.4 mmol) of N-dimethylthiocarbamate) was heated at 300 ° C. for 6 hours. After returning to room temperature and recrystallization from solid toluene, 0.55 g of 3-decyl-9- (phenylethynyl) dinaphtho [2,3-b: 2 ′, 3′-d] thiophene (yield, 73%) Got.
¹ H NMR (300 MHz, CDCl ₃ ): δ 8.677 (s, 1H), δ 8.663 (s, 1H), δ 8.179 (s, 1H), δ 8.152 (s, 1H), δ 8.094 (s) , 1H), δ 7.961-8.016 (m, 2H), δ 7.671 (s, 1H), δ 7.601 (dd, J = 1.5 Hz, 8.4 Hz, 1H), δ 7.567-7. .605 (m, 2H), δ 7.396 (dd, J = 1.8 Hz, 8.4 Hz, 1H), δ 7.367-7423 (m, 3H), δ 2.821 (t, J = 7. 2 Hz, 2H), δ1.617-1.778 (m, 2H), δ1.271-1.433 (m, 14H), δ0.898 (t, J = 6.6 Hz, 3H).
FD-MS: [M] ⁺ = 524.3

Synthesis Example 6 Synthesis of Compound (IV-22) in Chemical Formula 27

Under a nitrogen atmosphere, Advanced Materials, 2009, 21, 213-216. Nitrogen gas was bubbled while stirring 3.2 g (8.9 mmol) of 1,4-dibromo-2,5-bis (methyl sulfide) benzene synthesized by the method described in 45 mL of N, N-dimethylformamide at room temperature. Tetrakis (triphenylphosphine) palladium (0) 0.31 g (0.27 mmol) and tributyl (2-thienyl) tin 6.3 mL (19.6 mmol) were added, and the mixture was stirred at 100 ° C. for 46 hours in a nitrogen atmosphere. did. 70 mL of water was added to the reaction solution, extracted three times with 50 mL of chloroform, washed three times with 100 mL of saturated brine, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain a solid. This solid was dissolved in 150 mL of chloroform, and 30 g of a metal scavenger was added to prepare a slurry. The slurry was removed by filtration, and the filtrate was dried over anhydrous magnesium sulfate and then concentrated to dryness to obtain a crude solid. This crude solid was separated and purified by silica gel column chromatography (dichloromethane = 100), and 2.8 g (yield) of 2,2 ′-(2,5-bis (methylsulfinyl) -1,4-phenylene) dithiophene as a white solid. 73%).

To 2.5 g of 2,2 ′-(2,5-bis (methylsulfinyl) -1,4-phenylene) dithiophene, 0.35 g of diphosphorus pentoxide is added, 150 mL of trifluoromethanesulfonic acid is added, and under a nitrogen atmosphere Stir for 50 h. This reaction solution was slowly added to 800 mL of ice water, neutralized with 35% aqueous hydrochloric acid, and then a yellow solid was obtained by filtration. The obtained yellow solid was washed with water and filtered, and vacuum-dried at 40 ° C.

The yellow solid obtained by drying was added to 300 mL of pyridine, followed by stirring at 120 ° C. for 28 h under a nitrogen atmosphere. After concentrating this reaction solution, it was added to 500 mL of acetone, the precipitate was filtered off, chloroform was added, transferred to a separatory funnel, the machine layer was separated and washed with water and brine, dried over magnesium sulfate, Concentrated. The precipitate was dissolved in dichloromethane, separated and purified by a silica gel column (solvent composition: cyclohexane: dichloromethane = gradient of 50:50 to 0: 100), and yellow solid dithieno [2,3-d: 2 ′, 3 ′ -D ′] benzo [1,2-b: 4,5-b ′] dithiophene (hereinafter: TTBDT) 0.34 g (yield, 20%) was obtained.

To TTBDT (1.0 g, 3.3 mmol) was added 180 mL of dehydrated dichloromethane under an argon atmosphere, and the mixture was stirred for 30 minutes. Next, while cooling from −20 to −30 ° C., aluminum chloride (1.82 g, 13.2 mmol) was added in small portions while confirming the internal temperature, and octanoyl chloride (0.54 g, 3.3 mmol) was added at −70 ° C. ) Was added dropwise and stirred for 5 hours, and then the temperature of the reaction solution was raised to 0 ° C., and water was added to stop the reaction. Dichloromethane was added and transferred to a separatory funnel, and the organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The precipitate was separated and purified with a silica gel column (solvent composition: cyclohexane: chloroform = 100: 0 to 50:50 gradient), and yellow solid 2- (octyl-1-one) -TTBDT 0.4 g (yield, 28%).

To 2- (octyl-1-one) -TTBDT (1.27 g, 3.0 mmol), potassium hydroxide (0.51 g, 7.8 mmol) was added 120 mL of diethylene glycol, followed by hydrazine monohydrate (0.95 g , 18.9 mmol) was added and stirred while bubbling with nitrogen. Thereafter, the temperature was raised to 195 ° C. under a nitrogen atmosphere, and the mixture was stirred for 20 hours. After cooling to room temperature, water was added to the reaction solution to stop the reaction. The solid precipitated in the reaction solution was washed with water and methanol in this order. Dichloromethane was added to the washed solid and transferred to a separatory funnel, and the organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The precipitate was dissolved in dichloromethane and purified on a silica gel column (solvent composition: hexane: dichloromethane = 80: 20) to obtain 1.06 g of 2-octyl-TTBDT (yield 85%).

2-octyl-TTBDT 1.18 g (2.85 mmol) was dissolved in 80 mL of chloroform and then cooled to 0 ° C., and bromine 0.97 mL (3.56 mmol) was added dropwise over 20 minutes. The mixture was further stirred at 0 ° C. for 0.5 hour, then warmed to room temperature and stirred for 3 hours to stop the reaction. A 0.5 M aqueous sodium thiosulfate solution was added for liquid separation, and the lower layer was taken and concentrated to dryness to obtain a crude solid. This solid was recrystallized from an acetone / THF mixed solvent to obtain 0.51 g (yield, 36%) of 2-bromo-7-octyl-TTBDT white crystals.

Under an argon atmosphere, copper iodide 0.005 g (0.02 mmol), tetrakis (triphenylphosphine) palladium (0) 0.060 g (0.0052 mmol), 2-bromo-7-octyl-TTBDT 0.32 g (0.64 mmol) ) Was added with 15 mL of tetrahydrofuran and 0.6 mL of triethylamine, and stirred at room temperature. To the reaction solution, 0.2220 g (1.29 mmol) of p-ethynylpentylbenzene was added and stirred at 60 ° C. for 12 hours. After adding 50 mL of chloroform and washing with water, the organic phase was dried over magnesium sulfate and the solvent was distilled off. The obtained solid content was separated and purified by hot silica gel column chromatography (cyclohexane), and further recrystallized from acetone to give 153 mg of 2- (octyl) -7- (4- (pentylphenyl) ethynyl) -TTBDT (yield) 41.0%).
¹ HNMR (300 MHz, CDCl ₃ ): δ 8.11 (s, 1H), 7.78 (s, 1H), 7.43 (d, 2H), 7.20 (d, 2H) 7.11 (s, 1H), 6.96 (s, 1H), 2.612-2.691 (m, 4H), 1.585-1.648 (m, 4H), 1.383-1.510 (m, 14H) , 0.931-0.864m, 6H)
FD-MS: [M] ⁺ = 584.2

Synthesis Example 7 Synthesis of Compound (IV-42) in Chemical Formula 29

アルゴン雰囲気下、よう化銅０．００３３ｇ（０．０１７ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０）０．０３０ｇ（０．００２６ｍｍｏｌ）、２−（４−デシルフェニル）−７−ヨード−ナフト［２，１−ｂ：６，５−ｂ’］ジチオフェン０．２０６ｇ（０．３５４ｍｍｏｌ）にテトラヒドロフラン６ｍＬ、トリエチルアミン０．３ｍＬを加え、室温で撹拌した。反応液へｐ−エチニルペンチルベンゼン０．０８８７ｇ（０．５１５ｍｍｏｌ）を加え、６０℃で４時間撹拌した。クロロホルム５０ｍＬを加え、水洗した後、硫酸マグネシウムで有機相を乾燥、溶媒を留去した。得られた固形分を熱時シリカゲルカラムクロマトグラフィー（ヘキサン）で分離精製し２−（４−デシルフェニル）−７−（４−（ペンチルフェニル）エチニル）−ナフト［２，１−ｂ：６，５−ｂ’］ジチオフェン２０４ｍｇ（収率、９２．０％）を得た。
^１ＨＮＭＲ（３００ＭＨｚ，ＣＤＣｌ_３）δ８．３３２（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），δ８．１７５−８．２１４（ｍ，３Ｈ），δ７．９９１（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），δ７．９３２（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ）），δ７．７２１（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ）），δ７．５１５（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），δ７．２８６（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），δ７．２１３（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），２．６１２−２．６９１（ｍ，４Ｈ），１．５８５−１．６４８（ｍ，４Ｈ），１．３８３−１．５０３（ｍ，１８Ｈ），０．９３１−０．８６４（ｍ，６Ｈ）．
ＦＤ−ＭＳ：［Ｍ］^＋＝６２６．３

Under an argon atmosphere, 0.0033 g (0.017 mmol) of copper iodide, 0.030 g (0.0026 mmol) of tetrakis (triphenylphosphine) palladium (0), 2- (4-decylphenyl) -7-iodo-naphtho [ 2,1-b: 6,5-b ′] dithiophene (0.206 g, 0.354 mmol) was added with tetrahydrofuran (6 mL) and triethylamine (0.3 mL) and stirred at room temperature. To the reaction solution, 0.0887 g (0.515 mmol) of p-ethynylpentylbenzene was added and stirred at 60 ° C. for 4 hours. After adding 50 mL of chloroform and washing with water, the organic phase was dried over magnesium sulfate and the solvent was distilled off. The obtained solid was separated and purified by silica gel column chromatography (hexane) with heating to give 2- (4-decylphenyl) -7- (4- (pentylphenyl) ethynyl) -naphtho [2,1-b: 6, 204 mg (yield, 92.0%) of 5-b ′] dithiophene were obtained.
¹ HNMR (300 MHz, CDCl ₃ ) δ 8.332 (d, J = 8.7 Hz, 1H), δ 8.175-8.214 (m, 3H), δ 7.991 (d, J = 8.7 Hz, 1H) , Δ 7.932 (d, J = 8.7 Hz, 1H)), δ 7.721 (d, J = 8.1 Hz, 2H)), δ 7.515 (d, J = 8.1 Hz, 2H), δ7. 286 (d, J = 8.1 Hz, 2H), δ 7.213 (d, J = 8.1 Hz, 2H), 2.612-2.691 (m, 4H), 1.585-1.648 (m , 4H), 1.383-1.503 (m, 18H), 0.931-0.864 (m, 6H).
FD-MS: [M] ⁺ = 626.3

Synthesis Example 8 Synthesis of Compound (IV-41) in Chemical Formula 29

Under an argon atmosphere, dithieno [3,2-b: 2 ′, 3′-d] thiophene (1.09 g, 5.57 mmol), dehydrated dichloromethane 85 mL, decanoyl chloride (1.15 mL, 5.67 mmol) were added, Stir for 30 minutes. Next, the mixture was cooled to 0 ° C., and aluminum chloride (0.90 g, 6.73 mmol) was added in small portions while confirming the internal temperature. After stirring at room temperature for 1.5 hours, the reaction solution was cooled to 0 ° C., and water was added to stop the reaction. Dichloromethane was added and transferred to a separatory funnel, and the organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The precipitate was washed with hexane to obtain 1.91 g of 1- (dithieno [3,2-b: 2 ′, 3′-d] thiophen-2-yl) decan-1-one (yield 98%). .

1- (dithieno [3,2-b: 2 ′, 3′-d] thiophen-2-yl) decan-1-one (0.10 g, 0.29 mmol), potassium hydroxide (0.36 g, 6. 36 mmol), 3 mL of diethylene glycol was added, and then hydrazine monohydrate (0.5 mL, 10.3 mmol) was added and stirred while bubbling with nitrogen. Thereafter, the temperature was raised to 125 ° C. in a nitrogen atmosphere, and the mixture was stirred for 20 hours. After cooling to room temperature, water was added to the reaction solution to stop the reaction. The solid precipitated in the reaction solution was washed with water and methanol in this order. Dichloromethane was added to the washed solid and transferred to a separatory funnel, and the organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The precipitate is dissolved in dichloromethane and purified by a silica gel column (solvent composition is hexane: dichloromethane = 80: 20) to obtain 0.03 g of 2-decyldithieno [3,2-b: 2 ′, 3′-d] thiophene. (Yield 28%).

To 2-decyldithieno [3,2-b: 2 ', 3'-d] thiophene (0.26 g, 0.77 mmol), 3 mL of chloroform and 3 mL of acetic acid were added and stirred. After cooling the reaction solution to 0 ° C., N-bromosuccinimide (0.15 g, 0.83 mmol) was added in small portions while checking the internal temperature under light shielding. After stirring at room temperature for 2.5 hours, the reaction solution was cooled to 0 ° C., and an aqueous sodium hydrogen carbonate solution cooled with ice water was added to stop the reaction. Chloroform was added, the mixture was transferred to a separatory funnel, and the machine layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The solid was vacuum-dried at 60 ° C. to obtain 2-bromo-6-decyldithieno [3,2-b: 2 ′, 3′-d] thiophene (0.31 g, 0.74 mol) (yield 97%). ).

2-Bromo-6-decyldithieno [3,2-b: 2 ′, 3′-d] thiophene (0.15 g, 0.36 mmol), tetrakis (triphenylphosphine) palladium (0) (0.42 g,. (4-((4-pentylphenyl) ethynyl) phenyl) boronic acid (0.13 g, 0.43 mmol) obtained under the same conditions as those of Angelwandte Chemie, International Edition, 51 (11), 2623-2627 (2012) Under argon atmosphere, 8 mL of dehydrated tetrahydrofuran was added and stirred. Next, 0.7 mL of 2M sodium carbonate aqueous solution bubbled with argon was slowly added, and then the reaction solution was heated to 60 ° C. and stirred for 17 hours. After cooling to room temperature, water was added to the reaction solution to stop the reaction. Chloroform was added, the mixture was transferred to a separatory funnel, and the machine layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The precipitate was dissolved in chloroform and purified by a silica gel column (solvent composition: hexane: dichloromethane = 80: 20 to 50:50 gradient). After dissolving the solid in acetone heated to 50 ° C., a metal scavenger was added and stirred, the metal scavenger was removed by filtration, and recrystallized from the filtrate to give 2-decyl-6- (4-((4- 0.04 g of pentylphenyl) ethynyl) phenyl) dithieno [3,2-b: 2 ′, 3′-d] thiophene was obtained (19% yield).
¹ HNMR (300 MHz, CDCl ₃ ): δ 7.601 (d, J = 8.4 Hz, 2H), δ 7.535 (d, J = 8.7 Hz, 2H), δ 7.520 (s, 1H), δ7. 458 (d, J = 8.1 Hz, 2H)), δ 7.172 (d, J = 8.1 Hz, 2H)), δ 6.979 (s, 1H), δ 2.908 (t, J = 7.5 Hz) , 2H), δ 2.620 (t, J = 7.65 Hz, 2H) δ 1.778-1.690 (m, 2H), 1.675-1.559 (m, 2H), 1.378-1. 269 (m, 20H), 0.919-0.858 (m, 6H).
FD-MS: [M] ⁺ = 582.2

(Comparative Synthesis Example 1) Synthesis of dialkyl-substituted compound

In the synthesis of 2-decylnaphtho [2,1-b: 6,5-b ′] dithiophene of Synthesis Example 1, the crude product obtained by the reaction was separated and purified by silica gel column chromatography (hexane / chloroform = 95/5). Thus, 0.386 g of 2,7-didecylnaphtho [2,1-b: 6,5-b ′] dithiophene represented by the general formula (54), which was a by-product, was obtained.

(Comparative Synthesis Example 2) Synthesis of diphenyl-substituted compound

According to the synthesis method described in International Publication No. 2012/115236 pamphlet, 2,9-diphenyldinaphtho [2,3-b: 2 ′, 3′-f] thieno [3, represented by the general formula (55) 2-b] thiophene was obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

Example 1 Evaluation of Organic Transistor Characteristics of Compound of Synthesis Example 1 (Evaluation of Compound Solubility)
The p-xylene solution prepared so that the concentration of the compound obtained in Synthesis Example 1 was 0.4% by mass was heated to 60 ° C. to completely dissolve the compound. After the solution was stored at room temperature for 1 day, the presence or absence of a precipitate was visually confirmed, and it was confirmed that there was no precipitate. The solution thus obtained is hereinafter referred to as “p-xylene solution in which 0.4% by mass of the compound of Synthesis Example 1 is dissolved”.
In addition, regarding the solubility evaluation of the compound of the present invention, the case where there was no precipitate was indicated as ◯, the case where there was a precipitate was indicated as x, and the results are shown in Table 1.

(Manufacture and evaluation of TC transistors)
The TC transistor shown in FIG. 1 was manufactured as follows. First, the glass substrate was ultrasonically cleaned in this order with a neutral detergent aqueous solution, distilled water, acetone and ethanol (each 30 minutes × 3 times), and then a platinum film was formed by sputtering (film thickness: 30 nm). A gate electrode was prepared. Next, the glass substrate equipped with the platinum gate electrode is set in a thermal CVD apparatus (LABCOTERPDS2010, manufactured by Parylene, Japan), and a dichloro-di-p-xylylene polymer film (paraxylylene) having a film thickness of 1 μm under predetermined conditions. Ren polymer film) was prepared as a gate insulating layer. The substrate thus obtained is hereinafter referred to as “a glass substrate having a gate electrode and a gate insulating layer”.
Next, 0.05 μL of “p-xylene solution in which 0.4% by mass of the compound of Synthesis Example 1” was dropped on the “glass substrate including the gate electrode and the gate insulating layer”, and the semiconductor layer (channel Layer). Next, a source / drain electrode was formed on the substrate on which the semiconductor layer was formed by pattern deposition (vacuum deposition under 4 × 10 ⁻⁶ Torr) through a metal mask (film thickness: 30 nm, channel Length (L) / channel width (W): 100 μm / 1000 μm).
The transistor thus obtained was evaluated by applying a sweep voltage (V _sg : +40 to −60 V) to the gate electrode using a digital multimeter (SMU237, manufactured by Keithley) in an air atmosphere. The measurement was performed by measuring the current (I _d ) between the drain electrodes. The voltage (V _sd ) applied between the source and drain electrodes is −80V. As a result, the mobility was 1.1. The mobility was obtained from the slope of √I _d −V _sg using the following equation (iii). The unit is ^cm 2 / Vs.

（式中、μは移動度、Ｃはゲート絶縁層の単位面積当たりの電気容量、Ｖ_Ｔはゲート閾値電圧を表す。）

(Wherein μ represents mobility, C represents electric capacity per unit area of the gate insulating layer, and V _T represents gate threshold voltage.)

(Manufacture and evaluation of bottom contact (BC) type transistors)
The BC transistor shown in FIG. 2 was manufactured as follows.
On the “glass substrate having a gate electrode and a gate insulating layer”, gold was subjected to pattern deposition (vacuum deposition under 4 × 10 ⁻⁶ Torr) through a metal mask to form source / drain electrodes (film) Thickness: 30 nm, channel length (L) / channel width (W): 100 μm / 1000 μm). Next, the substrate on which the source / drain electrodes were formed was immersed in an ethanol solution of pentafluorobenzenethiol adjusted to 0.08 mass% for 1 hour, rinsed with ethanol, and then “the compound of Synthesis Example 1 was added. 0.05 μL of a 0.4 mass% dissolved p-xylene solution ”was dropped between the source electrode and the drain electrode to prepare a semiconductor layer (channel layer).
The characteristics of the transistor thus obtained were evaluated by the method described above, and as a result, the mobility was 1.8.

Example 2 Evaluation of Organic Transistor Characteristics of Compound of Synthesis Example 2 The same as Example 1 except that the compound obtained in Synthesis Example 2 was used in place of the compound obtained in Synthesis Example 1 as the material for the organic semiconductor layer. Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

Example 3 Evaluation of Organic Transistor Characteristics of Compound of Synthesis Example 3 As the material of the organic semiconductor layer, the same as Example 1 except that the compound obtained in Synthesis Example 3 was used instead of the compound obtained in Synthesis Example 1. Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

Example 4 Evaluation of Organic Transistor Characteristics of Compound of Synthesis Example 4 As Example 1 except that the compound obtained in Synthesis Example 4 was used instead of the compound obtained in Synthesis Example 1 as the material of the organic semiconductor layer. Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

(Example 5) Evaluation of organic transistor characteristics of compound of Synthesis Example 5 As the material of the organic semiconductor layer, the same as Example 1 except that the compound obtained in Synthesis Example 5 was used instead of the compound obtained in Synthesis Example 1. Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

Example 6 Evaluation of Organic Transistor Characteristics of Compound of Synthesis Example 6 As Example 1 except that the compound obtained in Synthesis Example 5 was used instead of the compound obtained in Synthesis Example 1 as the material of the organic semiconductor layer. Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

(Example 7) Evaluation of organic transistor characteristics of compound of synthesis example 7 As the material of the organic semiconductor layer, the compound obtained in synthesis example 5 was used instead of the compound obtained in synthesis example 1, and the same as in example 1 Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

(Example 8) Evaluation of organic transistor characteristics of compound of Synthesis Example 8 As the material of the organic semiconductor layer, the same as Example 1 except that the compound obtained in Synthesis Example 5 was used instead of the compound obtained in Synthesis Example 1. Then, TC and BC type transistors were fabricated and their characteristics were evaluated. The results are shown in Table 1.

(Comparative Example 1)
The solubility of the compound and the transistor characteristics were evaluated in the same manner as in Example 1 except that instead of the compound obtained in Synthesis Example 1 as the material for the organic semiconductor layer, the compound obtained in Comparative Synthesis Example 1 was used. It was. The results are shown in Table 1.

(Comparative Example 2)
When the compound obtained in Comparative Synthesis Example 2 was used in place of the compound obtained in Synthesis Example 1 as the material for the organic semiconductor layer and the solubility of the compound was evaluated in the same manner as in Example 1, the compound was found to be p. -It was not dissolved in xylene and the transistor could not be manufactured.

As is apparent from Table 1, the compound of the present invention is excellent in solvent solubility, and the known and conventional methods shown in Comparative Example 1 are used in both cases of a TC transistor and a BC transistor in which a semiconductor layer is simply formed by a wet method. It exhibits a higher mobility than that of the compound. Surprisingly, a BC type transistor that has been difficult to express characteristics conventionally exhibits higher characteristics than a TC type transistor. From the above, it is clear that the compound of the present invention has practically preferable performance as described above, and is superior to known and commonly used compounds.

The compound of the present invention can be used as an organic semiconductor, and can be used for an organic transistor using the organic semiconductor material as an organic semiconductor layer.

1: substrate, 2: gate electrode, 3: gate insulating layer, 4: organic semiconductor, 5: source electrode, 6: drain electrode

Claims (5)

A compound represented by general formula (1a), general formula (2a), general formula (3a), general formula (4a), general formula (5a), or general formula (6a).

(X represents an oxygen atom or a sulfur atom,
A ¹ Represents the general formula (7a),
R ₁ -C≡C- (R ₂ ) _p     (7a)
(R ₁ Represents a phenyl group, and one or more hydrogen atoms in the phenyl group are substituted with an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, a halogeno group, or a nitrile group. The alkyl group may be one or more —CH in the alkyl group. ₂ -Is optionally -O-, -CH = CH-, -CO-, -OCO-, -COO-, -S-, -SO so that the oxygen, sulfur and nitrogen atoms are not directly adjacent. ₂ -, -SO-, -NH-, -NR'- or -C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group are optionally substituted by a halogeno group or a nitrile group May be. (However, R 'represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms.)
R ₂ Is a phenylene group (-C ₆ H ₄ -) _p Represents an integer of 0 or 1. )

A ⁰ Represents a phenyl group having an alkyl group having 2 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms as a substituent. )
The organic-semiconductor material containing the compound in any one of Claim 1. An organic semiconductor ink containing the compound according to claim 1. An organic semiconductor device using the organic semiconductor material according to claim 2. An organic transistor using the organic semiconductor material according to claim 2.

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