JP6656506B2 - Benzothienobenzothiophene derivative, organic semiconductor material, and organic transistor - Google Patents

Description

  The present invention relates to a benzothienobenzothiophene derivative, an organic semiconductor material using the same, an organic semiconductor ink using the same, and an organic transistor using the same.

  A thin film transistor (TFT) using amorphous silicon or polycrystalline silicon as a semiconductor material is widely used as a switching element of a liquid crystal display device, an organic EL display device, or the like. However, since transistors using silicon have a high-temperature heat treatment process in their manufacture, they cannot be applied to next-generation flexible displays that use a plastic substrate due to the problem of heat resistance. In order to solve this, an organic transistor using an organic semiconductor material for a channel (semiconductor layer) instead of silicon has been proposed.

  Since an organic semiconductor material can be printed and formed at a low temperature by forming an ink, it can be applied to a plastic substrate having poor heat resistance, and is expected to be applied to a flexible display and further to a flexible electronics.

For example, Patent Documents 1 and ² disclose that a compound comprising an aromatic ring and an acetylene skeleton exhibits semiconductor characteristics (mobility) of 0.5 cm ² / Vs.

  On the other hand, these organic semiconductor materials have the initial problem of “organic semiconductors have lower semiconductor characteristics (mobility) than silicon semiconductors, and as a result, the response speed of transistors is slow and practical application is difficult”. Materials that exceed mobility are beginning to be developed.

For example, Patent Document 3 discloses that a compound having a dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene skeleton has a vacuum deposited film of 4.0 cm ² / Vs. Patent Document 4 discloses that a compound having a V-shaped structure having various substituents exhibits a high mobility of 11 cm ² / Vs in a single crystal thin film formed by an edge casting method. However, Non-Patent Document 1 discloses that 2,7-dioctyl [1] benzothieno [3,2-b] [1] benzothiophene is a single-crystal film manufactured by a double inkjet method and has a large variation in characteristics. , to exhibit high mobilities of up to 30 cm ² / Vs, also in Patent Document 5, naphthodifuran chalcogen compound of phenyl substitution indicate the mobility of 0.7 cm ² / Vs, Patent Document 6 7 has a higher order liquid crystal phase It is disclosed that the resulting compound exhibits a mobility of 5.7 cm ² / Vs in a thin film via a higher order liquid crystal phase. As described above, reports of organic semiconductor materials exhibiting semiconductor characteristics exceeding the mobility (0.5 cm ² / Vs) of amorphous silicon have been continuously made.

  Although the mobility of organic semiconductors is increasing in this way, it has not yet been put to practical use. This is because these disclosed mobilities were produced by a film forming method that gives a homogeneous bulk, such as a single crystal film by an edge casting method or a double inkjet method, a thin film by a vacuum evaporation method, a thin film by a spin coating method, and the like. It was evaluated using the film as a semiconductor layer. The polycrystalline film produced by dropping ink droplets (drop cast) and drying it, which leads to practical printing methods such as ink jet method and nozzle printing method This is because the characteristics of the semiconductor layer deteriorate.

International Publication No. 2009/125704 International Publication No. 2009/125721 International Publication No. WO 2012/115236 WO 2013/125599 International Publication No. WO 2010/058692 International Publication No. 2012/121393 International Publication No. WO 2014/038708

Nature, 2011, 475, 364

  Since conventional organic semiconductor materials have poor solubility in solvents, it is difficult to prepare ink, and therefore, there has been a problem in wet film formation leading to printing. Materials with solvent solubility also have problems in producing uniform films, such as disordered molecular arrangement during wet film formation and partial crystallization. Therefore, a complicated film forming method and a complicated post-film forming process (such as an annealing process) are required.

  Therefore, an object of the present invention is to provide a film having high mobility, which has excellent solubility in a solvent and can be easily formed without passing through a complicated process (that is, simply by dropping ink droplets and drying the ink droplets). It is an object of the present invention to provide a compound to be provided and an organic semiconductor material using the same, and further provide an organic semiconductor ink which can easily produce an organic transistor having a practical configuration.

  The present inventors have conducted intensive studies to achieve the above object, and a heterocyclic aromatic compound having a specific structure having a substituent composed of a specific arylene acetylene structure is suitable as an organic semiconductor ink because of its excellent solvent solubility. That does not require complicated heat treatment and provides a high mobility organic semiconductor film even by a simple wet method (that is, a method of simply dropping ink droplets and drying itself). This led to the completion of the present invention.

That is, the present invention includes the following items.
1. General formula (1)

(Wherein, R ₁ is any group of (I), and R ₂ is a group selected from any group of (II).
(I) a group represented by the general formula (2) or (3)

(Ar ₁ is an aromatic hydrocarbon group or a heteroaromatic group having an alkyl group having 2 to 18 carbon atoms as a substituent, and the aromatic hydrocarbon group or the heteroaromatic group is a monocyclic or heterocyclic group. Ar ₂ is an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group which may have a substituent; R ′ is a hydrogen atom; To 20 to 20 alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups which may have a substituent.)
(II) a group selected from a hydrogen atom, a methyl group, a cyano group, a fluoro group, and a trifluoromethyl group. )
A benzothienobenzothiophene derivative represented by
2. The following general formula (4)

(Wherein, R ₁ is a group represented by the following general formula (2) or (3);

(However, Ar ₁ , Ar ₂ and R ′ are as defined above.)
R ₂ is a group selected from a hydrogen atom, a methyl group, a cyano group, a fluoro group, and a trifluoromethyl group. )
1. represented by A benzothienobenzothiophene derivative according to
3. 1. Or 2. Organic semiconductor material using the benzothienobenzothiophene derivative according to
4. 3. Organic semiconductor ink containing the organic semiconductor material according to,
5. 3. Organic semiconductor film containing the organic semiconductor material according to,
6. 3. Organic semiconductor element using the organic semiconductor material according to the,
7. 3. An organic transistor using the organic semiconductor material described in 1 above as an organic semiconductor layer.
8. A method for producing a benzothienobenzothiophene derivative represented by the general formula (5),

(In the formula, Ar ₃ is an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, wherein the aromatic hydrocarbon group or the heteroaromatic group is monocyclic or has 2 or more rings. 3 is a polycyclic group, and R ₃ represents a group selected from a hydrogen atom, an alkyl group, a cyano group, a fluoro group, and a trifluoromethyl group.)
(1) The compound represented by the general formula (6) is reacted with a carboxylic acid chloride (Cl—CO—Ar ₃ (where Ar ₃ has the same meaning as described above)) and expressed by the general formula (7). Obtaining the compound to be obtained;
(2) a step of reacting a compound represented by the general formula (7) with a metal salt of trialkylsilyldiazomethane to obtain a compound represented by the general formula (5);
And a manufacturing method.

(In the formula, R ₃ has the same meaning as described above.)

(In the formula, R ₃ and Ar ₃ are as defined above.)

  According to the present invention, a compound having excellent solubility in a solvent and exhibiting high mobility, an organic semiconductor material containing the compound, an organic semiconductor ink containing the compound, and an organic transistor containing the compound are provided. Can be.

FIG. 3 is a schematic cross-sectional view of a bottom-gate bottom-contact transistor.

(Compound)
The compound of the present invention has a benzothienobenzothiophene ([1] benzothieno [3,2-b] [1] benzothiophene; hereinafter abbreviated as BTBT) as represented by the general formula (1) or (4). A compound having R ₁ and R ₂ as substituents on a ring, wherein at least one of the substituents is a group represented by the general formula (2) or (3) having a specific arylene acetylene structure; Is characterized in that the substituent is a group selected from a hydrogen atom, a methyl group, a cyano group, a fluoro group and a trifluoromethyl group.

(Wherein, R ₁ is any group of (I), and R ₂ is a group selected from any group of (II).
(I) a group represented by the general formula (2) or the general formula (3)

(Ar ₁ is an aromatic hydrocarbon group or a heteroaromatic group having an alkyl group having 2 to 18 carbon atoms as a substituent, and the aromatic hydrocarbon group or the heteroaromatic group is a monocyclic or heterocyclic group. Ar ₂ is an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group which may have a substituent; R ′ is a hydrogen atom; To 20 to 20 alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups which may have a substituent.)
(II) a group selected from a hydrogen atom, a methyl group, a cyano group, a fluoro group, and a trifluoromethyl group. )

  In the compound of the present invention, the main skeleton containing a BTBT ring is connected to an aromatic ring or the like via an acetylene moiety, whereby the solvent solubility is improved, and the mobility is further improved by expanding a π-conjugate plane.

  Further, by shortening one of the substituents such as a hydrogen atom, a methyl group, a cyano group, a fluoro group, and a trifluoromethyl group, the interaction between the substituents is simplified and a uniform semiconductor film is provided. Becomes possible. That is, even with a simple wet method of “dropping ink droplets and drying them”, it is possible to provide an organic semiconductor film with high mobility.

  Next, the substituent of the compound of the present invention will be described.

Substituents R ₂ in the general formula (1) compounds represented by the present invention, a hydrogen atom, a methyl group, a cyano group, fluoro group, a group selected from a trifluoromethyl group.

Meanwhile, the substituent R ₁ of the compound represented by the general formula (1) of the present invention is a substituent represented by the general formula (2) or (3).

Ar ₁ of the substituent represented by the general formula (2) is an aromatic hydrocarbon group or a heteroaromatic group having an alkyl group having 2 to 18 carbon atoms as a substituent, and the aromatic hydrocarbon group or The heteroaromatic group is not particularly limited as long as it is a monocyclic group or a polycyclic group having 2 or 3 rings, and examples thereof include the following.

  Examples of the aromatic hydrocarbon group having an alkyl group having 2 to 18 carbon atoms as a substituent include a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, an acenaphthenyl group, an anthracenyl group, a phenanthryl group and a naphthacenyl group. And monocyclic or polycyclic aromatic hydrocarbon groups having 6 to 24 carbon atoms, such as fluorenyl, pyrenyl, chrysenyl, perylenyl, biphenyl, p-terphenyl, and quarterphenyl groups.

Specific examples of the aromatic hydrocarbon group (Ar ₁ ) having an alkyl group having 2 to 18 carbon atoms as a substituent include a 4-ethylphenyl group, a 4-n-propylphenyl group, a 4-isopropylphenyl group, and a 4-isopropylphenyl group. n-butylphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n- Examples include a decylphenyl group and a 9,9′-dihexylfluorenyl group, but are not limited thereto.

  Examples of the heteroaromatic group of the heteroaromatic group having an alkyl group having 2 to 18 carbon atoms as a substituent include a pyrrolyl group, an indolyl group, a furyl group, a thienyl group, a bithienyl group, a terthienyl group, a quarterthienyl group, and a thienothienyl. Group, imidazolyl group, benzofuryl group, triazolyl group, benzotriazolyl group, benzothienyl group, pyrazolyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, indolinyl group, thiazolyl Group, pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, thiadiazinyl group, oxadiazolyl group, benzoquinolinyl group, thiadiazolyl group, pyrrolothiazolyl group, pyrrolopyridazinyl group, tetrazolyl group, oxazolyl group, bithienyl group Examples thereof include a 5-membered or 6-membered heteroaromatic group such as a terthienyl group and a quarterthienyl group, and a polycyclic heteroaromatic group in which another aromatic group is condensed to the heteroaromatic group. .

Specific examples of the heteroaromatic group (Ar ₁ ) having a C 2 to C 18 alkyl group as a substituent include a 5-ethylthienyl group, a 5-n-propylthienyl group, a 5-isopropylthienyl group, and a 5-n -Butylthienyl group, 5-n-pentylthienyl group, 5-n-hexylthienyl group, 5-n-heptylthienyl group, 5-n-octylthienyl group, 5-n-nonylthienyl group, 5-n-decylthienyl group And the like.

Among the above, from the viewpoint of solvent solubility, Ar ₁ is preferably a phenyl group, a naphthyl group, a biphenyl group, a thienyl group, or a benzothienyl group having an alkyl group having 2 to 18 carbon atoms as a substituent. From the viewpoint, an aromatic hydrocarbon group or a heteroaromatic group having an alkyl group having 2 to 10 carbon atoms as a substituent is preferable, and therefore, from the viewpoints of solvent solubility and semiconductor properties, both have 2 to 10 carbon atoms. A phenyl group, a naphthyl group, a biphenyl group, a thienyl group, and a benzothienyl group each having an alkyl group as a substituent are particularly preferred.

Ar ₂ of the substituent represented by the general formula (3) is not particularly limited as long as it is an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group which may have a substituent. However, for example, the following can be mentioned.

A phenylene group, a naphthylene group, an azulylene group, an acenaphthenylene group, an anthracenylene group, a phenanthrenylene group, a naphthacenylene group, a fluorenylene group, a pyrenylene group, a chrysenylene group, a perylenylene group, a biphenylene group, a p-terphenylene group, a quarterphenylene group, etc. A monocyclic or polycyclic aromatic hydrocarbon divalent group having 6 to 24 carbon atoms,
Tolylene group, xylylene group, ethylphenylene group, propylphenylene group, isopropylphenylene group, butylphenylene group, pentylphenylene group, hexylphenylene group, heptylphenylene group, octylphenylene group, nonylphenylene group, decylphenylene group, methylnaphthylene, An alkyl-substituted aromatic hydrocarbon divalent group in which the aromatic hydrocarbon divalent group is substituted with an alkyl group having 2 to 18 carbon atoms, such as a 9,9′-dihexylfluorenyl group;
Such as a fluorophenylene group, a chlorophenylene group, a bromophenylene group, or the like, wherein the aromatic hydrocarbon divalent group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; No.

  Further, a heteroaromatic divalent group such as thienylene and pyridylene, or a heteroaromatic divalent group substituted with such a heteroaromatic divalent group can also be used.

  R ′ of the substituent represented by the general formula (3) is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group. Although there is no particular limitation, for example, the following are mentioned.

  Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, -Methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n-octyl group, tert-octyl Group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethyl Hexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n Straight-chain such as tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, cycloheptyl, cyclooctyl, etc. Chain, branched or cyclic alkyl group,

Examples of the aromatic hydrocarbon group which may have a substituent include phenyl, naphthyl, azulenyl, acenaphthenyl, anthranyl, phenanthryl, naphthacenyl, fluorenyl, pyrenyl, chrysenyl, perylenyl, biphenyl A monocyclic or polycyclic aromatic hydrocarbon group having 6 to 24 carbon atoms, such as a group, a p-terphenyl group, or a quarterphenyl group;
o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, mesityl group, juryl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4 -Isopropylphenyl group, 4-n-butylphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-decaphenyl group, 4-stearylphenyl group, 9,9'-dihexylfur An alkyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkyl group having 1 to 18 carbon atoms, such as an olenyl group;
An alkenyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkenyl group having 2 to 20 carbon atoms, such as a styryl group, a 4-butenylphenyl group, and a 4-octadecenylphenyl group;

The aromatic hydrocarbon group such as a 4-fluorophenyl group, a 2,6-fluorophenyl group, a 4-chlorophenyl group, a 2,3,4,5,6-perfluorophenyl group is a fluorine atom, a chlorine atom, or a bromine; A halogenated aromatic hydrocarbon group substituted with a halogen such as an atom,
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 and the like, wherein the aromatic hydrocarbon group has 3 to 20 carbon atoms. An alkoxyalkyl-substituted aromatic hydrocarbon group substituted with an alkoxyalkyl group of

A 4- (methylsulfanylpropyl) phenyl group, a 4- (2-n-hexylsulfanylethyl) phenyl group, a 4- (3-n-decylsulfanylpropyl) phenyl group, a 4- (cyclohexylsulfanylpropyl) phenyl group, etc. An alkylsulfanylalkyl-substituted aromatic hydrocarbon group in which the aromatic hydrocarbon group is substituted with an alkylsulfanylalkyl group having 3 to 20 carbon atoms,
The aromatic hydrocarbon group is an alkylamino having 3 to 20 carbon atoms, such as a 4- (3-octylaminopropyl) phenyl group, a 4- (3-dodecylaminopropyl) phenyl group, and a 4- (diethylaminoethyl) phenyl group; And an alkylaminoalkyl-substituted aromatic hydrocarbon group substituted with an alkyl group.

Examples of the heteroaromatic group which may have a substituent include a pyrrolyl group, an indolyl group, a furyl group, a thienyl group, an imidazolyl group, a benzofuryl group, a triazolyl group, a benzotriazolyl group, a benzothienyl group, and a pyrazolyl group. , Indolizinyl group, quinolinyl group, isoquinolinyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, indolinyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, thiadiazinyl group, oxadiazolyl group, benzoquinolinyl group, 5- or 6-membered heteroaromatic groups such as thiadiazolyl, pyrrolothiazolyl, pyrrolopyridazinyl, tetrazolyl and oxazolyl groups, and polycyclic heteroaromatics in which benzene is fused to the heteroaromatic group Group,
An alkyl-substituted heteroaromatic group in which the heteroaromatic group such as a 5-methylthienyl group, a 5-hexylthienyl group, a 5-decathienyl group, or a 5-stearylthienyl group is substituted with an alkyl group having 1 to 20 carbon atoms;

5- (2-ethoxyethyl) thienyl, a halogenated heteroaromatic group in which the above heteroaromatic group such as a fluoropyridinyl group and a fluoroindolyl group is substituted with a halogen such as a fluorine atom, a chlorine atom and a bromine atom A 5- (2-n-tetradecyloxyethyl) thienyl group,
An alkoxyalkyl-substituted heteroaromatic in which the aromatic hydrocarbon group is substituted with an alkoxyalkyl group having 3 to 20 carbon atoms, such as a 5- (2-cyclohexyloxyethyl) thienyl group and a 5- (12-ethoxydodecyl) thienyl group. Group,

A 5- (methylsulfanylpropyl) thienyl group, a 5- (2-n-hexylsulfanylethyl) thienyl group, a 5- (3-n-decylsulfanylpropyl) thienyl group, a 5- (cyclohexylsulfanylpropyl) thienyl group, etc. An alkylsulfanylalkyl-substituted heteroaromatic group in which an aromatic hydrocarbon group is substituted with an alkylsulfanylalkyl group having 3 to 20 carbon atoms,
The heteroaromatic group is an alkylaminoalkyl having 3 to 20 carbon atoms, such as a 5- (3-octylaminopropyl) thienyl group, a 5- (3-dodecylaminopropyl) thienyl group, or a 5- (diethylaminoethyl) thienyl group; And an alkylaminoalkyl-substituted heteroaromatic group substituted with a group.

  Specific compounds of the present invention having the substituents described above include, but are not limited to, the following.

(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.
One example of a synthetic route is shown below, but the synthesis of the compound of the present invention is not limited to these.

First, BTBT ring as a base skeleton, the reaction (A) ~ to as (D), as a group corresponding to substituent R _2, introducing a methyl group, a cyano group, fluoro group, or a trifluoromethyl group .

  In the synthesis of compound (a-2), first, BTBT is formylated to obtain compound (a-1). Next, this is methylated by a reduction reaction.

  In the synthesis of compound (b-2), first, BTBT is brominated to obtain compound (b-1). Next, this is trifluoromethylated by reacting it with a Barton reagent in the presence of a copper (I) salt.

  In the synthesis of compound (c-3), first, BTBT is nitrated to obtain compound (c-1). Next, this is subjected to a reduction reaction, and thereafter, copper cyanide is allowed to act thereon (Zandmeyer reaction).

  In the synthesis of the compound (d-1), the compound (c-2) is converted to diazonium fluoroborate, which is thermally decomposed.

Introduction of a substituent R ₂ of the BTBT ring, here is not limited to the reaction (A) ~ (D) indicated, it can be applied to the reaction conventionally known.

Next, BTBT (e-1) having R ₂ (hydrogen atom, methyl group, cyano group, fluoro group, trifluoromethyl group) as a substituent is reacted with a carboxylic acid chloride, acylated, and then acylated. By reacting the metal salt of alkylsilyldiazomethane, the target compound (e-3) having a substituent represented by the general formula (2) as R ₁ can be obtained (reaction (E)). Here, examples of the trialkylsilyl group in the “metal salt of trialkylsilyldiazomethane” include, for example, a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, and a triisopropylsilyl group. is there. Examples of the metal forming the metal salt in the “metal salt of trialkylsilyldiazomethane” include, for example, lithium, sodium, magnesium, zinc and aluminum, and preferably lithium.

(In the formula, R ₂ and Ar ₁ are as defined above.)
The reaction (E) can be applied to the case where R ₂ is an alkyl group. In addition to the case where Ar ₁ is the above-mentioned substituent, an unsubstituted aromatic hydrocarbon group or heteroaromatic group The present invention is also applicable to an aromatic hydrocarbon group or a heteroaromatic group having an aromatic group or a methyl group (an alkyl group having 1 carbon atom) as a substituent.

BTBT (f-1) having R ₂ (hydrogen atom, methyl group, cyano group, fluoro group, trifluoromethyl group) as a substituent is reacted with a halogenating agent, and halogenated (f-2); Then, by subjecting the organoboron compound to cross-coupling in the presence of a palladium catalyst and a base, the target compound (f-3) having a substituent represented by the general formula (3) as R ₁ can be obtained. (Reaction (F)).

(In the formula, R ₂ , Ar ₂ and R ′ have the same meanings as described above, and X represents a halogen atom.)
Incidentally, introduction of a substituent R ₁ to BTBT ring, here indicated reaction (E) ~ is not limited to (F), it can be applied to the reaction conventionally known.

(Organic semiconductor materials and inks)
The compound of the present invention can be used as an organic semiconductor material for an organic semiconductor device. In order to use the compound of the present invention as an organic semiconductor, it is usually used in the form of a film (organic semiconductor film or organic semiconductor layer). In forming the film, it may be formed by a known and commonly used dry film forming method such as vacuum deposition, but it is preferable to form the film by a printing method capable of forming a film at a low temperature and having excellent productivity. The compounds of the invention, ie, organic semiconductor materials, are preferably used as inks. In order to prepare an ink, the compound of the present invention is dissolved in a solvent. In addition, in order to impart ink properties within a range that does not impair the semiconductor performance, a fluorine-based or silicon-based leveling agent, and a polymer compound such as polystyrene, an acrylic resin, or a semiconductor polymer are added as a viscosity modifier. Can also.

Any solvent may be used, or two or more solvents may be used as a mixture. 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, 2,5-diethylsibenzene, chlorobenzene, o-dichlorobenzene Aromatic solvents such as trichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, ethylene glycol diethyl ether, anisole, benzyl ethyl ether, ethyl phenyl ether, diphenyl ether and methyl-t-butyl ether; methyl acetate, ethyl acetate, ethyl cellosolve; Ester solvents such as propylene glycol methyl ether acetate; alcohol solvents such as methanol, ethanol and isopropanol; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-hexanone, 2-heptanone and 3-heptanone; other dimethylformamide and dimethyl Examples include, but are not limited to, sulfoxide, diethylformamide, and the like.
The concentration of the compound of the present invention in the prepared liquid composition is preferably from 0.01 to 20% by weight, and more preferably from 0.1 to 10% by weight.

(Organic semiconductor device)
Examples of the organic semiconductor element using the compound of the present invention as an organic semiconductor material include a diode, an organic transistor, a photodiode, a light emitting diode, a light emitting transistor, a gas sensor, a biosensor, a blood sensor, an immunosensor, an artificial retina, and a taste sensor. And the like, and further, a memory, an RFID, and the like.
Among them, the compound of the present invention has a high charge mobility of 1 cm ² / Vs or more as an organic semiconductor material, and thus is particularly useful for application to an organic transistor or a light-emitting element.

(Organic transistor)
Next, an organic transistor using the organic semiconductor material of the present invention as an organic semiconductor layer will be described.
An organic transistor generally has a source electrode, a drain electrode and a gate electrode, a gate insulating layer, and an organic semiconductor layer. There are various types of transistors depending on the arrangement of each electrode and each layer. The organic semiconductor material described above can be used for any transistor without being limited to the type of transistor. For the types of transistors, reference can be made to Aldrich's Material Science Fundamentals No. 6, "Basics of Organic Transistors".

  The bottom contact type shown in FIG. 1 will be described in detail as an example. 1 is a substrate, 2 is a gate electrode, 3 is a gate insulating layer, 4 is an organic semiconductor layer, 5 is a source electrode, and 6 is a drain electrode.

  As the substrate, glass, resin, or plastic is used. To obtain a flexible organic transistor, a glass sheet, a resin sheet, or a plastic film can be used. Among them, the use of a resin sheet or a plastic film is preferable because it can reduce the weight in addition to the flexibility, improve the portability, and improve the resistance to impact. Examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Triacetate (TAC) and cellulose acetate propionate (CAP) can be exemplified.

The electrode material of the gate electrode, the source electrode, and the drain electrode is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, tin oxide, antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, carbon, graphite, glassy carbon, silver paste, 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 / aluminum mixture And the like can be used. Further, known conductive polymers having improved conductivity by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylene dioxythiophene and polystyrene sulfonic acid (PEDOT / PSS), and the like are also suitable. Used.

  As a method of forming an electrode, a method of patterning a conductive thin film formed using a material such as the above as a raw material by a method such as evaporation or sputtering, using a known photolithographic method or a lift-off method, or on the conductive thin film In addition, there is a method in which a resist is formed into a pattern by thermal transfer or ink jet, and then etched. Further, a solution or dispersion of a conductive polymer or a dispersion of conductive fine particles may be directly patterned by inkjet, or a solution or dispersion of a conductive polymer or a dispersion or paste of conductive fine particles may be applied. The coating film thus obtained may be patterned by lithography or laser ablation. Furthermore, the conductive polymer solution or dispersion or the conductive fine particle dispersion or paste is patterned by various printing methods such as a screen printing method, an offset printing method, a letterpress printing method, a reverse printing method, and a microcontact printing method. Can also be used.

  The gate insulating layer is made of a thermoplastic resin such as polyparaxylylene, polystyrene, acrylic resin, or polyester resin; a thermosetting resin such as epoxy resin, urethane resin, phenol resin, unsaturated polyester resin, alkyd resin, or melamine resin; An organic thin film such as a curable resin can be suitably used, and an inorganic material such as a silicon oxide film can also be used.

  The gate insulating layer is formed by spin coating, casting, dip coating, doctor blade coating, wire bar coating, spray coating, dispensing, inkjet printing, screen printing, gravure printing, offset printing, letterpress printing, inversion. A thin film can be formed by a known wet film forming method such as a printing method, a micro contact print method, or the like, and may be patterned into a required shape by a photolithographic method as needed.

  The organic semiconductor layer can be formed by a known and common dry film formation method such as a vacuum evaporation method using the compound of the present invention, and the wet film formation method such as printing using the ink of the present invention. It is preferable to form a film by using The thickness of the organic semiconductor layer is not particularly limited, but is usually 0.5 nm to 1 μm, and preferably 2 nm to 250 nm.

  The organic semiconductor layer may be subjected to annealing after film formation, if necessary, for the purpose of improving crystallinity and improving semiconductor characteristics. The annealing temperature is preferably from 50 to 200 ° C, more preferably from 70 to 200 ° C, and the time is preferably from 10 minutes to 12 hours, more preferably from 1 hour to 10 hours, even more preferably from 30 minutes to 10 hours. .

  Examples of the film forming method include a spin coating method, a casting method, a dip method, a doctor blade method, a wire bar coating method, a spray coating method, a dispensing method, an ink jet method, a screen printing method, a gravure printing method, an offset printing method, and a relief printing method. Known wet film formation methods such as a printing method, a reverse printing method, and a microcontact printing method can be used.

  The organic transistor of the present invention can be suitably used as a switching transistor of a pixel constituting a display, a signal driver circuit element, a memory circuit element, a signal processing circuit element, and the like. Examples of the display include a liquid crystal display, a dispersion liquid crystal display, an electrophoretic display, a particle rotating display device, an electrochromic display, an organic electroluminescent display, and electronic paper.

The present invention will be described in more detail with reference to examples.
(Example 1) <Production of compound>
First, 30 mL of dehydrated dichloromethane was added to BTBT (0.51 g, 2.12 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (1.10 g, 8.25 mmol) was added, and p-propylbenzoyl chloride (0.35 mL, 1.99 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 1.5 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. For purification, the product collected on a silica gel column (solvent composition: hexane: dichloromethane = 100: 0 to 30:70 gradient) was recrystallized with acetone to obtain 0.45 g of 2- (4-propylbenzoyl) BTBT ( Yield 55%).

  Next, a 2 M solution of trimethylsilyldiazomethane (1.20 mL, 2.40 mmol) was added to 13.5 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.50 mL, 2.33 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2- (4-propylbenzoyl) BTBT (0.44 g, 1.14 mmol) to which 4 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 1.5 hours. Then, a 10% acetic acid methanol solution was added to stop the reaction. Dichloromethane was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. For purification, the product recovered by a silica gel column (solvent composition: hexane: dichloromethane = 100: 0 to 90:10 gradient) is dissolved in acetone heated to 56 ° C., a metal scavenger is added, the mixture is stirred, and the metal scavenger is separated by filtration. By removing and recrystallizing from the filtrate, 0.04 g of the BTBT derivative represented by (I) was obtained (yield 9%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.09 (s, 1H, BTBT ring), 7.94-7.88 (dd, 2H, BTBT ring), 7.86 (d, 1H, BTBT ring) , 7.60 (d, 1H, BTBT ring), 7.50-7.47 (dd, 2H, phenyl), 7.46-7.40 (dd, 2H, BTBT ring), 7.18 (d, 2H, _{phenyl), 2.62 (t, 2H,} BTBT-CH 2), 1.66 (q, 2H, BTBT-CH 2 -CH 2), 0.96 (t, 3H, CH 3).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.09 (1 H, d, J = 1.1 Hz), 7.94-7.83 (3 H, m), 7.62-7.59 (1 H, m), 7.50-7.39 (4H, m), 7.19 (2H, d, J = 8.4 Hz), 2.62 (2H, t, J = 7.5 Hz), 1.66 ( 2H, td, J = 15.0, 7.5 Hz), 0.96 (3H, t, J = 7.3 Hz).
FD-MS: [M] ⁺ = 382

<Manufacture of organic transistors>
Using a metal mask, aluminum was deposited on a glass substrate (corresponding to 1 in FIG. 1) to a thickness of about 30 nm by a vacuum evaporation method to form a gate electrode (corresponding to 2 in FIG. 1). Here, using a parylene vapor deposition apparatus (Lab Coater PDS2010, manufactured by Nippon Parylene), using polychloro-diparaxylylene (DPX-C, manufactured by Nippon Parylene) as a raw material, polyparachloroxylylene (Parylene C) thin film (500 nm thick) Was formed by a chemical vapor deposition (CVD) method (corresponding to 3 in FIG. 1), and further, a source / drain electrode composed of a gold thin film (40 nm in thickness) was patterned by a vacuum evaporation method (FIG. 1). 5 and 6. The channel length L (source electrode-drain electrode distance) was 75 μm, and the channel width W was 5.0 mm. Next, the substrate thus obtained was immersed in a 0.1% ethanol solution of pentafluorothiophenol for 1 hour, and then dried by blowing with nitrogen to obtain 0.4% of the compound BTBT derivative compound (I). After drop-casting (dropping) 0.1 μL of a p-xylene solution (organic semiconductor ink) between the source / drain electrodes, the compound BTBT derivative compound (I) is allowed to dry by natural concentration. An organic semiconductor layer (corresponding to 4 in FIG. 1) was formed (organic semiconductor layer was formed by dropping (drop casting) of an organic semiconductor solution (ink) droplet and drying it).

<Evaluation of semiconductor characteristics (mobility)>
The semiconductor characteristics (mobility) of the organic transistor thus obtained were evaluated. Semiconductor characteristics (mobility) is grounded source electrode, while applying a -80V to the drain electrode, a digital multimeter (SMU237, Keithley Co.) using, -80V from 0 to the gate electrode, the voltage _{(V g} ) while sweeping applying, to measure the current _{(I d)} flowing to the drain electrode, the slope of √I _d -V _g, was determined using the equation (1). The unit is cm ² / V · s.

(Where W is the channel width, L is the channel length, μ is the mobility, C is the electric capacity per unit area of the gate insulating layer, and _VT is the threshold voltage.)
Table 1 shows the evaluation results.

(Example 2) <Production of compound>
First, 35 mL of dehydrated dichloromethane was added to BTBT (0.50 g, 2.08 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (1.16 g, 8.70 mmol) was added, and p-pentylbenzoyl chloride (0.5 mL, 2.46 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 4 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. For purification, the product recovered on a silica gel column (solvent composition: hexane: dichloromethane = 100: 0 to 30:70 gradient) was recrystallized from cyclohexane to obtain 0.49 g of 2- (4-pentylbenzoyl) BTBT ( Yield 57%).

Then, a 2 M solution of trimethylsilyldiazomethane (1.20 mL, 2.40 mmol) was added to 10 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.50 mL, 2.33 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2- (4-pentylbenzoyl) BTBT (0.49 g, 1.18 mmol) to which 7 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 3.5 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Dichloromethane was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification is performed by recrystallizing a product recovered by a silica gel column (a product obtained by sprinkling silica gel and a metal scavenger with cyclohexane heated to 55 ° C.) with acetone to obtain B represented by (II).
0.06 g of a TBT derivative was obtained (13% yield).

¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.08 (1H, dd, J = 4.4, 3.7 Hz), 7.87 (3H, ddt, J = 19.3, 11.0, 3) 7.6 Hz), 7.61-7.56 (1H, m), 7.49-7.39 (4H, m), 7.19 (2H, d, J = 8.1 Hz), 2.63 (2H) , T, J = 7.1 Hz), 1.68-1.58 (2H, m), 1.34 (4H, dt, J = 12.6, 5.0 Hz), 0.90 (3H, dd, J = 9.0, 5.0 Hz).
FD-MS: [M] ⁺ = 410

<Manufacture of organic transistor and evaluation of semiconductor characteristics (mobility)>
Production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1 except that the compound (II) was used instead of the compound (I). Table 1 shows the results.

(Example 3) <Production of compound>
First, 25 mL of dehydrated dichloromethane was added to BTBT (0.50 g, 2.09 mmol) and aluminum chloride (1.16 g, 8.70 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to −70 ° C., and p-heptylbenzoyl chloride (0.70 mL, 1.45 mmol) was added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 3 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. For purification, the product recovered on a silica gel column (solvent composition: hexane: dichloromethane = 100: 0 to 30:70 gradient) was recrystallized with acetone to obtain 0.39 g of 2- (4-heptylbenzoyl) BTBT ( Yield 39%).

Then, a 2M solution of trimethylsilyldiazomethane (0.85 mL, 2.07 mmol) was added to 5 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.0 mL, 1.55 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2- (4-heptylbenzoyl) BTBT (0.36 g, 0.82 mmol) to which 12 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 3 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Dichloromethane was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. For purification, the product collected on a silica gel column (solvent composition: hexane: dichloromethane = 100: 0 to 90:10 gradient) is dissolved in acetone heated to 56 ° C, a metal scavenger is added, and the mixture is stirred, and the metal scavenger is separated by filtration. By removing and recrystallizing from the filtrate, 0.04 g of a BTBT derivative represented by the compound (III) was obtained (yield: 11%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.09 (1H, d, J = 0.7 Hz), 7.94-7.83 (3H, m), 7.60 (1H, dd, J = 8.3, 1.3 Hz), 7.49-7.40 (4H, m), 7.19 (2H, d, J = 8.1 Hz), 2.63 (2H, t, J = 7.7 Hz) ), 1.60-1.56 (2H, m), 1.31 (8H, m), 0.89 (3H, t, J = 6.8 Hz).
FD-MS: [M] ⁺ = 438

<Manufacture of organic transistor and evaluation of semiconductor characteristics (mobility)>
Production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1 except that the compound (III) was used instead of the compound (I). Table 1 shows the results.

(Example 4) <Production of compound>
First, 35 mL of dehydrated dichloromethane was added to BTBT (0.50 g, 2.08 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (1.13 g, 8.48 mmol) was added, and further p-decylbenzoyl chloride (0.6 mL, 2.14 mmol) was added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 3 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. For purification, the product recovered on a silica gel column (solvent composition: hexane: dichloromethane = 100: 0 to 30:70 gradient) was recrystallized from cyclohexane to obtain 0.54 g of 2- (4-decylbenzoyl) BTBT ( Yield 54%).

Then, a 2M solution of trimethylsilyldiazomethane (1.10 mL, 2.20 mmol) was added to 10 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.40 mL, 2.17 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2- (4-decylbenzoyl) BTBT (0.54 g, 1.11 mmol) to which 6 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 4 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Dichloromethane was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The BTBT derivative represented by the compound (IV) is purified by recrystallizing the product recovered by a silica gel column (a product obtained by sprinkling silica gel and a metal scavenger with cyclohexane heated at 55 ° C.) using acetone. Was obtained (yield 21%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.08 (1H, t, J = 3.1 Hz), 7.94-7.81 (3H, m), 7.60 (1H, dd, J = 8.1, 1.5 Hz), 7.50-7.39 (4H, m), 7.18 (2H, d, J = 8.1 Hz), 2.63 (2H, t, J = 7.7 Hz) ), 1.60 (2H, t, J = 7.3 Hz), 1.29 (14H, m), 0.88 (3H, t, J = 6.6 Hz).
FD-MS: [M] ⁺ = 480

<Manufacture of organic transistor and evaluation of semiconductor characteristics (mobility)>
Production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1 except that the compound (IV) was used instead of the compound (I). Table 1 shows the results.

(Example 5) <Production of compound>
25 mL of dehydrated dichloromethane was added to 2-methylBTBT (0.50 g, 2.08 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (1.12 g, 8.40 mmol) was added, and p-propylbenzoyl chloride (0.5 mL, 2.84 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 2 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification was performed using a silica gel column (solvent composition: hexane: dichloromethane = 90: 10 to 50:50 gradient) to obtain 0.54 g of 2-methyl-7- (4-propylbenzoyl) BTBT (yield 64%). .

Next, a 2 M solution of trimethylsilyldiazomethane (1.35 mL, 2.70 mmol) was added to 4.5 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.75 mL, 2.71 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2-methyl-7- (4-propylbenzoyl) BTBT (0.54 g, 1.34 mmol) to which 21 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 2.5 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The BTBT derivative represented by the compound (V) is purified by recrystallizing a product recovered by a silica gel column (a product sprinkled on silica gel and a metal scavenger with cyclohexane heated to 55 ° C.) using acetone. Was obtained (yield 23%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.07 (1 H, d, J = 0.7 Hz), 7.76 (3 H, dt, J = 17.6, 6.8 Hz), 7.58 ( 1H, dd, J = 8.4 Hz, 1.5 Hz), 7.48 (2H, t, J = 4.2 Hz), 7.28 (1H, t, J = 2.8 Hz), 7.18 (2H , D, J = 8.1 Hz), 2.61 (2H, t, J = 7.5 Hz), 2.52 (3H, s), 1.66 (2H, td, J = 15.0, 7.0). 3 Hz), 1.66 (2H, td, J = 15.0, 7.3 Hz), 0.95 (3H, t, J = 7.3 Hz).
FD-MS: [M] ⁺ = 396

<Manufacture of organic transistor and evaluation of semiconductor characteristics (mobility)>
Production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1 except that the compound (V) was used instead of the compound (I). Table 1 shows the results.

(Example 6) <Production of compound>
First, 210 mL of dehydrated dichloromethane was added to BTBT (2.51 g, 10.4 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (6.09 g, 45.7 mmol) was added, and butyldichloromethyl ether (2.0 mL, 14.1 mmol) was further added dropwise. After stirring for 2.5 hours, the reaction solution was reprecipitated in water to stop the reaction. A saturated aqueous sodium hydrogen carbonate solution was added thereto to neutralize. Chloroform was further added, the mixture was transferred to a separating funnel, and the organic layer was separated and washed with water and brine, dried over magnesium sulfate and concentrated. Purification was performed using a silica gel column (solvent composition: hexane: dichloromethane = 90: 10 to 10:90 gradient) to obtain 1.33 g of 2-formyl BTBT (yield 47%).

  Next, 10 mL of dehydrated dichloromethane was added to aluminum chloride (0.89 g, 6.68 mmol) under an argon atmosphere, followed by stirring. The mixture was further cooled to 0 ° C., tert-butylamine borane (1.16 g, 13.3 mmol) was added, and the atmosphere was replaced with argon again.

  After stirring for 5 minutes, a 2-formyl BTBT (0.60 g, 2.24 mmol) solution to which 20 mL of dehydrated dichloromethane was added was added to the reaction solution. After stirring for 1 hour, the reaction solution was reprecipitated in water to stop the reaction. Dilute hydrochloric acid was added thereto to neutralize. Further, chloroform was added, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification was performed on a silica gel column (solvent composition: hexane: dichloromethane = 95: 5 to 50:50 gradient) to obtain 0.28 g of 2-methylBTBT (yield 49%).

  25 mL of dehydrated dichloromethane was added to 2-methylBTBT (0.51 g, 2.12 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (1.14 g, 8.55 mmol) was added, and p-pentylbenzoyl chloride (0.5 mL, 2.46 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 2 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification was performed using a silica gel column (solvent composition: hexane: dichloromethane = 90: 10 to 50:50 gradient) to obtain 0.47 g of 2-methyl-7- (4-pentylbenzoyl) BTBT (yield: 52%). .

Next, a 2M solution of trimethylsilyldiazomethane (1.00 mL, 2.00 mmol) was added to 4.5 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.50 mL, 2.33 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2-methyl-7- (4-pentylbenzoyl) BTBT (0.47 g, 1.10 mmol) to which 21 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 2 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The BTBT derivative represented by the compound (VI) is purified by recrystallizing the product recovered by a silica gel column (a product obtained by sprinkling silica gel and a metal scavenger with cyclohexane heated at 55 ° C.) using acetone. Was obtained (yield 21%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.06 (1H, t, J = 3.7 Hz), 7.82-7.75 (2H, m), 7.72 (1H, s), 7 0.76-7.55 (1H, m), 7.46 (2H, t, J = 7.7 Hz), 7.29 (1H, d, J = 0.7 Hz), 7.18 (2H, d, J = 8.1 Hz), 2.63 (2H, t, J = 7.7 Hz), 2.51 (3H, d, J = 7.3 Hz), 1.68-1.58 (2H, m), 1.36 (4H, ddd, J = 20.4, 10.5, 4.9 Hz), 0.90 (3H, t, J = 7.0 Hz).
FD-MS: [M] ⁺ = 424

<Manufacture of organic transistor and evaluation of semiconductor characteristics (mobility)>
Production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1 except that the compound (VI) was used instead of the compound (I). Table 1 shows the results.

(Example 7) <Production of compound>
20 mL of dehydrated dichloromethane was added to 2-methylBTBT (0.40 g, 1.66 mmol) under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (0.90 g, 6.73 mmol) was added, and p-heptylbenzoyl chloride (0.5 mL, 2.10 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 2.5 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification was performed using a silica gel column (solvent composition: hexane: dichloromethane = 90: 10 to 50:50 gradient) to obtain 0.54 g of 2-methyl-7- (4-heptylbenzoyl) BTBT (yield 71%). .

Then, a 2M solution of trimethylsilyldiazomethane (1.20 mL, 2.40 mmol) was added to 4.5 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (1.50 mL, 2.33 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2-methyl-7- (4-heptylbenzoyl) BTBT (0.54 g, 1.19 mmol) to which 21 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 2.5 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The BTBT derivative represented by the compound (VII) is purified by recrystallizing a product recovered by a silica gel column (a product sprinkled on silica gel and a metal scavenger with cyclohexane heated to 55 ° C.) using acetone. Was obtained (yield 24%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.05 (1H, t, J = 3.3 Hz), 7.81-7.71 (3H, m), 7.57 (1H, dt, J = 10.5 Hz, 3.8 Hz), 7.46 (2H, t, J = 7.3 Hz), 7.29 (1 H, d, J = 0.7 Hz), 7.17 (2H, t, J = 7) .3 Hz), 2.66 (2H, dd, J = 23.3, 16.0 Hz), 2.51 (3H, d, J = 6.6 Hz), 1.61 (2H, dd, J = 14. 7,7.3 Hz), 1.30 (8H, dd, J = 7.2, 5.0 Hz), 0.89 (3H, t, J = 6.8 Hz).
FD-MS: [M] ⁺ = 452

<Manufacture of organic transistor and evaluation of semiconductor characteristics (mobility)>
Production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1 except that compound (VII) was used instead of compound (I). Table 1 shows the results.

(Example 8) <Production of compound>
25 mL of dehydrated dichloromethane was added to 2-decyl BTBT (0.50 g, 1.31 mmol) synthesized according to Patent Document 7 under an argon atmosphere, followed by stirring. Next, the mixture was cooled to -70 ° C, aluminum chloride (0.70 g, 5.25 mmol) was added, and benzoyl chloride (0.2 mL, 1.45 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 2 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification was performed using a silica gel column (solvent composition: hexane: dichloromethane = 90: 10 to 50:50 gradient) to obtain 0.35 g of 2-decyl-7-benzoyl BTBT (55% yield).

Next, a 2 M solution of trimethylsilyldiazomethane (0.72 mL, 1.44 mmol) was added to 4 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (0.93 mL, 1.44 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2-decyl-7-benzoylBTBT (0.35 g, 0.72 mmol) to which 7 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 2.5 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The BTBT derivative represented by (VIII) was purified by recrystallizing the product recovered by a silica gel column (a product obtained by sprinkling silica gel and a metal scavenger with cyclohexane heated at 55 ° C.) using acetone. 0.09 g was obtained (yield 25%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.08 (1 H, d, J = 1.8 Hz), 7.83 (1 H, d, J = 8.2 Hz), 7.78 (1 H, d, J = 7.8 Hz), 7.72 (1H, s), 7.61-7.55 (3H, m), 7.38-7.35 (3H, m), 7.29 (1H, dd, J = 7.8 Hz), 2.77 (2H, t, J = 7 Hz), 1.70 (2H, quint., J = 7 Hz), 1.55-1.27 (14H, m, J = 15. 0, 7.3 Hz), 0.88 (3H, t, J = 7 Hz).
FD-MS: [M] ⁺ = 480.3

(Example 9) <Production of compound>
25 mL of dehydrated dichloromethane was added to 2-decyl BTBT (0.50 g, 1.31 mmol) synthesized according to Patent Document 7 under an argon atmosphere, followed by stirring. Next, the mixture was cooled to −70 ° C., aluminum chloride (0.70 g, 5.25 mmol) was added, and p-toluoyl chloride (0.2 mL, 1.45 mmol) was further added dropwise. After the temperature of the reaction solution was raised to 0 ° C. and stirred for 2 hours, the reaction solution was reprecipitated in water to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. Purification was performed using a silica gel column (solvent composition: hexane: dichloromethane = 90: 10 to 50:50 gradient) to obtain 0.36 g of 2-decyl-7- (4-toluoyl) BTBT (57% yield).

Next, a 2 M solution of trimethylsilyldiazomethane (0.72 mL, 1.44 mmol) was added to 4 mL of dehydrated tetrahydrofuran under an argon atmosphere, followed by stirring. The mixture was further cooled to −70 ° C., and a 1.55 M n-butyllithium solution (0.93 mL, 1.44 mmol) was added dropwise to generate a lithium salt of trimethylsilyldiazomethane. After stirring for 30 minutes, a solution of 2-decyl-7- (p-toluoyl) BTBT (0.36 g, 0.72 mmol) to which 7 mL of dehydrated tetrahydrofuran was added was added to the reaction solution. Thereafter, the reaction solution was heated to room temperature and stirred for 2.5 hours, and then a 10% acetic acid methanol solution was added to stop the reaction. Chloroform was added thereto, and the mixture was transferred to a separating funnel. The organic layer was separated and washed with water and brine, dried over magnesium sulfate, and concentrated. The BTBT derivative represented by (IX) was purified by recrystallizing the product recovered by a silica gel column (a product obtained by sprinkling silica gel and a metal scavenger with cyclohexane heated at 55 ° C.) using acetone. 0.09 g was obtained (yield 24%).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.08 (1 H, d, J = 1.8 Hz), 7.83 (1 H, d, J = 8.2 Hz), 7.78 (1 H, d, J = 7.8 Hz), 7.72 (1H, s), 7.57 (1H, dd, J = 8.2 Hz), 7.44 (2H, d), 7.29 (1H, dd, J = 7.8 Hz), 7.16 (2H, d), 2.77 (2H, t, J = 7 Hz), 2.37 (3H, s), 1.70 (2H, quint., J = 7 Hz), 1.55-1.27 (14H, m, J = 15.0, 7.3 Hz), 0.88 (3H, t, J = 7 Hz).
FD-MS: [M] ⁺ = 494.3

(Comparative Example 1)
The compound represented by (I ′) was synthesized by the method described in WO 2006/077888. For the obtained compound, production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 2)
The compound represented by (II ′) was synthesized by the method described in WO 2009/125721. For the obtained compound, production of an organic transistor and evaluation of semiconductor characteristics (mobility) were performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 3)
The compound represented by (III ′) was synthesized by the method described in International Publication No. WO 2014/038708. Table 1 shows the results of the evaluation of the solubility and the transistor evaluation of the obtained compound in the same manner as in the examples.

  From the results in Table 1, it can be seen that the compound of the present invention has high solvent solubility and high homogeneity of the polycrystalline film to be applied. Even when a semiconductor layer is formed, an organic transistor having high semiconductor characteristics (mobility) is provided. On the other hand, the compound of the comparative example has low semiconductor characteristics (mobility) in the film formation method.

  The compound of the present invention can be used as an organic semiconductor material, 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 layer, 5: source electrode, 6: drain electrode

Claims (7)

General formula (1)

(Wherein, R ₁ is any group of (I), and R ₂ is a group selected from any group of (II).
(I) a group represented by the general formula (2) or (3)

(Ar ₁ is an aromatic hydrocarbon group or a heteroaromatic group having an alkyl group having 2 to 18 carbon atoms as a substituent, and the aromatic hydrocarbon group or the heteroaromatic group is a monocyclic or heterocyclic group. Ar ₂ is an aromatic hydrocarbon group which may have a substituent or a heteroaromatic group which may have a substituent; R ′ is a hydrogen atom; To 20 to 20 alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups which may have a substituent.)
(II) a group selected from a hydrogen atom, a methyl group, a cyano group, a fluoro group, and a trifluoromethyl group. )
A benzothienobenzothiophene derivative represented by the formula: The following general formula (4)

(Wherein, R ₁ is a group represented by the following general formula (2) or (3);

(However, Ar ₁ , Ar ₂ and R ′ are as defined above.)
R ₂ is a group selected from a hydrogen atom, a methyl group, a cyano group, a fluoro group, and a trifluoromethyl group. )
The benzothienobenzothiophene derivative according to claim 1, which is represented by:   An organic semiconductor material using the benzothienobenzothiophene derivative according to claim 1.   An organic semiconductor ink containing the organic semiconductor material according to claim 3.   An organic semiconductor film containing the organic semiconductor material according to claim 3.   An organic semiconductor device using the organic semiconductor material according to claim 3.   An organic transistor using the organic semiconductor material according to claim 3 as an organic semiconductor layer.

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