JP2017052721A - Organic compound, manufacturing method thereof, organic semiconductor material containing the same and organic transistor containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound excellent in solubility to a solvent and easily providing a film exhibiting high mobility without passing complicated process, an organic semiconductor material using the same and further an organic semiconductor ink capable of easily manufacturing an organic transistor having a practical constitution.SOLUTION: There is provided a manufacturing method of a dithienobenzodithiophene derivative having following processes. (I) a first process of converting a compound represented by the general formula (B) to an organic metallic compound (B)' having Xas an active part. (II) a second process of manufacturing a compound represented by the general formula (D) by cross coupling the organic metal compound (B)' and a compound represented by the general formula (C). (III) a third process of converting a compound represented by the general formula (E) to an organic metal compound (E)' having Xas an active part. (IV) a fourth process of manufacturing a compound represented by the general formula (F) by cross coupling the organic metal compound (E)' and a compound represented by the general formula (D).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dithienobenzodithiophene derivative, a production method thereof, an organic semiconductor material containing the same, an organic semiconductor ink containing the same, and an organic transistor containing the same.

  Thin film transistors (TFTs) using amorphous silicon or polycrystalline silicon as a material are widely used as switching elements in liquid crystal display devices and organic EL display devices. However, these transistors using silicon materials use an expensive CVD apparatus or the like in the manufacture thereof, so that the manufacturing cost increases when the size is increased. In addition, since the silicon material is formed at a high temperature, it cannot be developed in a next-generation flexible electronic device that uses a plastic substrate due to the problem of heat resistance. In order to solve this problem, an organic transistor using an organic semiconductor material for a channel (semiconductor layer) instead of a silicon semiconductor material has been proposed.

Organic semiconductor materials can be printed at low temperatures by converting them into inks, so they do not require large-scale and expensive manufacturing equipment, and can also be applied to plastic substrates with poor heat resistance. Is expected.
Furthermore, these organic semiconductor materials initially had problems such as “semiconductor characteristics (mobility) are lower than silicon semiconductor materials, which slows the response speed of transistors and is difficult to put into practical use”. Materials that surpass the mobility of amorphous silicon have begun to be developed.

For example, Patent Document 1 discloses that a compound having a dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene skeleton has a vacuum deposition film of 4.0 cm ² / Vs. to exhibit mobility, Patent Document 2 and 3, dinaphtho [2,3- b: 2 ', 3' -d] thiophene derivative, 11cm single-crystal thin film formed by the edge casting ² / Non-Patent Document 1 shows that a high mobility of Vs is shown in Non-Patent Document 1, in which a single crystal film in which 2,7-dioctyl [1] benzothieno [3,2-b] [1] benzothiophene is manufactured by a double inkjet method in, to exhibit high mobilities of up to 30 cm 2 / ^Vs ones what large variation in characteristics, Patent Document 4, naphthodifuran chalcogen compound of phenyl substitution indicate the mobility of 0.7 cm 2 / ^Vs In Patent Documents 5 to 6, It is disclosed that a compound that expresses a high-order liquid crystal phase exhibits a mobility of 5.7 cm ² / Vs in a thin film via a high-order liquid crystal phase. As described above, there are a number of reports on organic semiconductor materials exhibiting semiconductor characteristics exceeding the mobility (0.5 cm ² / Vs) of amorphous silicon.

  Thus, although the mobility of organic semiconductors is increasing, it has not yet been put into practical use. This is produced by using a film formation method in which these disclosed mobility gives a uniform bulk, such as a single crystal film by an edge casting method or a double ink jet method, a thin film by a vacuum deposition method, a thin film by a spin coating method, etc. Polycrystals produced by dropping ink droplets (drop casting) and drying them, which were evaluated using the applied film as a semiconductor layer and lead to practical printing methods such as the inkjet method and nozzle printing method. This is because characteristics of the semiconductor layer made of a film are deteriorated.

  Furthermore, as will be described later, in practical use, it is desired that a bottom gate bottom contact type (BC type) element structure exhibit high characteristics (reason: BC type is a material constituting a transistor (insulation). Among the materials, conductive materials, and semiconductor materials), since the organic semiconductor with the lowest heat resistance is formed in the last step, the organic semiconductor is hardly affected by heat)) This is derived from a bottom gate top contact type (TC type) element structure.

  The dithienobenzodithiophene derivatives of the present invention are disclosed in the examples of Patent Documents 7 to 12 in which the dithienobenzodithiophene derivatives having different substituent position structures are disclosed. There is no description.

International Publication No. 2012/115236 International Publication No. 2013/125599 JP 2007-197400 A International Publication No. 2010/058692 International Publication No. 2012/121393 International Publication No. 2014/038708 JP2013-035814A JP 2009-054810 A JP2013-189434A Special table 2014-515727 Special table 2011-526588 JP2012-206953

Nature, 2011, 475, 364.

  Since conventional organic semiconductor materials have poor solubility in solvents, it is difficult to adjust ink, and thus there has been a problem in wet film formation leading to printing. In addition, materials with solvent solubility also have problems in the production of homogeneous films, such as disorder of molecular arrangement during wet film formation and partial crystallization. However, a difficult film formation method and a complicated post film formation process (annealing process, etc.) are required.

  Accordingly, an object of the present invention is a film that exhibits excellent mobility in a solvent and exhibits high mobility easily without passing through a complicated process (that is, simply dropping ink droplets and drying them). It is to provide an organic semiconductor ink that can easily produce an organic transistor having a practical configuration.

  In order to achieve the above object, the present inventor has intensively studied and a dithienobenzodithiophene derivative having a specific substituent position structure has suitability as an organic semiconductor ink because it has excellent solvent solubility, and is complicated. Even a simple and practical wet film formation method (ie, a method of “dropping ink droplets and drying them”) provides an organic semiconductor film with high mobility without requiring any special treatment. As a result, the present invention has been completed.

That is, the present invention includes the following items.
1. A method for producing a dithienobenzodithiophene derivative represented by the general formula (A), which comprises the following steps (I) to (IV):
(I) a first step of converting a compound represented by the general formula (B) into an organometallic compound (B) ′ having X ₅ as an active site;
(II) a second step of producing a compound represented by the general formula (D) by cross-coupling the organometallic compound (B) ′ with the compound represented by the general formula (C);
(III) a third step of converting the compound represented by the general formula (E) into an organometallic compound (E) ′ having X ₇ as an active site;
(IV) A fourth step of producing a compound represented by the general formula (F) by cross-coupling the organometallic compound (E) ′ with the compound represented by the general formula (D).

(In each formula, X _{1 to} X ₈ represent a halogen atom, and R ₂ , R ₃ , R ₅ , R ₇ , R ₈ and R ₁₀ represent a hydrogen atom or an arbitrary substituent.)
2. R ₂ , R ₃ , R ₅ , R ₇ , R ₈ and R ₁₀ are each independently a hydrogen atom, an acyclic or cyclic alkyl group having 1 to 20 carbon atoms (- In order that CH ₂ — is not directly bonded to an oxygen atom, a sulfur atom, or a nitrogen atom, —O—, —R′C═CR′—, —CO—, —OCO—, —COO—, —S—, _{-SO 2 -, - SO -,} - NH -, - NR'- or -C≡C- may be substituted with a hydrogen atom in the alkyl group, a substituted aromatic group, the halogeno group, or a nitrile group (Wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms)), a halogeno group, an aromatic group (the aromatic group may be acyclic or cyclic). Substituted with an alkyl group of 1 to 20 carbon atoms, a halogeno group, an aromatic group, or a nitrile group of the formula Ku, -CH ₂ in the alkyl group - is an oxygen atom, such sulfur atoms and nitrogen atoms are not bonded each directly, -O -, - CR '' = CR '' -, - CO -, - OCO- , —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR ″ — or —C≡C—, and the hydrogen atom in the alkyl group is aromatic Group, halogeno group, or nitrile group (where R ″ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms)), a nitro group, or a nitrile group Yes, The production method according to
3. For R ₂ , R ₃ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₂ and R ₇ are the same or different, R ₃ and R ₈ are the same or different, and R ₅ and R ₁₀ are the same, At least one of the two combinations of R ₂ and R ₇ and R ₃ and R ₈ is different from each other. Or 2. The production method according to
4). A method for producing a dithienobenzodithiophene derivative represented by the general formula (G), which comprises the following steps (I) to (III):
(I) a first step of producing a compound represented by the general formula (I) by monohalogenating a compound represented by the general formula (H) in the presence of N-halosuccinimide;
(II) A compound represented by general formula (I) and a compound represented by general formula (J) or general formula (K) are subjected to a cross-coupling reaction in the presence of a transition metal catalyst, A second step for producing the compound represented,
(III) The compound represented by the general formula (L) is subjected to catalytic hydrogen reduction in the presence of a heterogeneous transition metal catalyst or a homogeneous transition metal catalyst to obtain a dithienobenzodithiophene derivative represented by the general formula (G). The third step to manufacture,

(In each formula, R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ represent a hydrogen atom or an arbitrary substituent, X ₁₁ represents a halogen atom, and Y ₁₁ − represents CH ₃ — (CH ₂ ) _n−2 −. C≡C— or CH ₃ — (CH ₂ ) _n−2 —CH═CH—, where n represents an integer of 2 to 19.
5. A method for producing a dithienobenzodithiophene derivative represented by the general formula (M), wherein the dithienobenzodithiophene derivative represented by the general formula (G) ′ is represented by the general formula (m) in the presence of organolithium. A process for producing a dithienobenzodithiophene derivative represented by the general formula (M), comprising a step of reacting an alkyl halide to produce a dithienobenzodithiophene derivative represented by the general formula (M);

(In each formula, R ₁₀₂ represents an alkyl group having 1 to 20 carbon atoms, R ₁₀₇ represents an alkyl group having 1 to 20 carbon atoms, and R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ are hydrogen atoms or Represents an arbitrary substituent, and X ₁₂ represents a halogen atom, provided that R ₁₀₂ and R ₁₀₇ are different.
6). A dithienobenzodithiophene derivative represented by the general formula (N),

(In the formula, R ₂₂ represents a linear alkyl group having 2 to 20 carbon atoms, and R ₂₇ represents a hydrogen atom or a methyl group.)
7.6. An organic semiconductor material containing the dithienobenzodithiophene derivative according to claim 1,
8.7. An organic semiconductor ink containing the organic semiconductor material according to claim 1,
9.7. An organic semiconductor film containing the organic semiconductor material described in
10.7. An organic semiconductor element comprising the organic semiconductor material according to claim 1,
11.7. An organic transistor containing the organic semiconductor material described in 1.

  According to the present invention, high mobility can be achieved by a simple and practical wet film forming method (that is, a method of simply “dropping ink droplets and drying them”) with excellent solubility in a solvent. A dithienobenzodithiophene derivative having a specific substituent position structure that gives an organic semiconductor film, a method for producing the dithienobenzodithiophene derivative, an organic semiconductor material containing the derivative, an organic semiconductor ink containing the derivative, and the derivative An organic transistor can be provided.

It is a conceptual diagram of a bottom gate bottom contact type (BC type) transistor. It is a conceptual diagram of a bottom gate top contact type (TC type) transistor.

(Method for producing dithienobenzodithiophene derivative)
A method for producing the dithienobenzodithiophene derivative of the present invention will be described.
<Production method 1 of the present invention>
The production method of the present invention comprises:
It is a manufacturing method of the dithienobenzodithiophene derivative represented by general formula (A), Comprising: It has the manufacturing process as described in (I)-(IV) below, It is characterized by the above-mentioned.
(I) a first step of converting a compound represented by the general formula (B) into an organometallic compound (B) ′ having X ₅ as an active site;
(II) a second step of producing a compound represented by the general formula (D) by cross-coupling the organometallic compound (B) ′ with the compound represented by the general formula (C);
(III) a third step of converting the compound represented by the general formula (E) into an organometallic compound (E) ′ having X ₇ as an active site;
(IV) A fourth step of producing a compound represented by the general formula (F) by cross-coupling the organometallic compound (E) ′ with the compound represented by the general formula (D).

(In each formula, X _{1 to} X ₈ represent a halogen atom, and R ₂ , R ₃ , R ₅ , R ₇ , R ₈ and R ₁₀ represent a hydrogen atom or an arbitrary substituent.)

The substituents R ₂ , R ₃ , R ₅ , R ₇ , R ₈ and R ₁₀ of the compounds represented by the general formulas (A) to (F) relating to the production method of the present invention are each independently aromatic. As the substituent of the compound, a known and commonly used substituent (however, an inert substituent that does not become a reaction active part in the production process described later) can be used. As a specific example,
A hydrogen atom (including light hydrogen, deuterium and tritium),
An acyclic or cyclic alkyl group having 1 to 20 carbon atoms (in which —CH ₂ — in the alkyl group is —O—, —R so that an oxygen atom, a sulfur atom and a nitrogen atom are not directly bonded to each other); 'C = CR' -, - CO -, - OCO -, - COO -, - S -, - SO 2 -, - SO -, - NH -, - NR'- or -C≡C- substituted with The hydrogen atom in the alkyl group may be substituted with an aromatic group, a halogeno group, or a nitrile group (provided that R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms). )), A halogeno group, an aromatic group (the aromatic group is substituted with an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, a halogeno group, an aromatic group, or a nitrile group. In the alkyl group, —CH ₂ — may be directly bonded to an oxygen atom, a sulfur atom and a nitrogen atom. Not to focus, -O -, - CR '' = CR '' -, - CO -, - OCO -, - COO -, - S -, - SO 2 -, - SO -, - NH -, - NR ″-Or —C≡C— may be substituted, and a hydrogen atom in the alkyl group may be substituted by an aromatic group, a halogeno group, or a nitrile group (provided that R ″ is a carbon atom) And a non-cyclic or cyclic alkyl group of 1 to 20))), a nitro group, or a nitrile group.

Among these substituents,
Preferably,
A hydrogen atom, an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, a fluoro (F) group, an aromatic group, a nitro group, or a nitrile group,
More preferably,
A hydrogen atom, or an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, more preferably,
It is a hydrogen atom or an acyclic alkyl group having 1 to 20 carbon atoms.

Specific examples of the acyclic alkyl group having 1 to 20 carbon atoms include
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 1-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-trimethylhexyl group, n-decyl group, n-undecyl Group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- eicosyl group and the like can be mentioned

The position configuration of the substituents (combination of substituents), taking advantage of the features of this manufacturing method, the _{"R 2, R 3, R 5} , R 7, R 8, R 10, R 5 and _{R 10} are the same Yes, R ₂ and R ₇ are the same or different, R ₃ and R ₈ are the same or different, and at least one of the two combinations of R ₂ and R ₇ , R ₃ and R ₈ is different from each other. In some cases.

Next, the effect of this manufacturing method will be described.
In a known and commonly used method for producing a dithienobenzodithiophene derivative (Japanese Patent Laid-Open No. 2014-22498), 2 equivalents or more of dihalothiophene is allowed to act on 1,4-difluoro-2,5-dibromobenzene in the first step, and then The dithienobenzothiophene derivative is obtained in a point-symmetric state. Therefore, in this known and conventional method, only a derivative in which R ₂ and R ₇ are the same and R ₃ and R ₈ are the same as the positional structure of the substituent (combination of substituents) is produced due to the nature of the method. I can't. On the other hand, in this production method, “R ₂ , R ₃ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₂ and R ₇ are the same or different, and R ₃ and R ₈ are the same or different, R ₅ and R ₁₀ are the same, and a dithienobenzodithiophene derivative in which at least one of two combinations of R ₂ and R ₇ , R ₃ and R ₈ is different from each other can be produced. . As will be described later, such a derivative is excellent in solvent solubility due to the loss of symmetry, and therefore has suitability as an organic semiconductor ink, and further, because the aggregation property is controlled, In addition, an organic semiconductor film having high semiconductor properties (mobility) can be provided by a practical wet film forming method (that is, a method of simply “dropping ink droplets and drying the ink itself”). (Described in dithienobenzodithiophene derivative of the present invention).

First, the first step will be described.
First step, a compound represented by the formula (B), and a step of converting the organometallic compound to X ₅ and the active site (B) '.
Many of the compounds represented by formula (B) are commercially available and are easily available. It can also be synthesized by the method described in Journal of Materials Chemistry, 2009, Vol. 19, pages 5913-5915. Compound (B), when directed to an organic metal compound was X ₅ and the reaction point, boron-substituted group used in a general cross-coupling reaction, silicon substituents, tin substituents, magnesium substituents, zinc substituent Etc. can be introduced. In order to efficiently perform the stepwise reaction under mild conditions, it is more preferable to perform the Negishi reaction using a zinc substituent.

Examples of the boron substituent that can be used include a boronyl group (B (OH) ₂ ), an ester derivative of a boronyl group, and a borabicyclo [3.3.1] nonanyl group (9-BBN). Examples of the silicon substituent include an arylsilyl group, a haloalkylsilyl group, and an alkoxysilyl group. Examples of the tin substituent include a trialkylstannyl group. Examples of the magnesium substituent include a magnesium fluoro group (MgF), a magnesium chloro group (MgCl), a magnesium bromo group (MgBr), and a magnesium iodo group (MgI). Examples of the zinc substituent include zinc fluoro group (ZnF), zinc chloro group (ZnCl), zinc bromo group (ZnBr), and zinc iodide group (ZnI).

  The molar ratio between the compound represented by the general formula (B) and the various reactants for deriving the organometallic compound is not particularly limited as long as the compound (B) ′ can be obtained. -2.0, preferably 0.9-1.2, more preferably 0.95-1.05.

The reaction temperature is not particularly limited as long as compound (B) ′ is obtained, and is −100 to 100 ° C., preferably −80 to 40 ° C.
The reaction time is not particularly limited as long as compound (B) ′ is obtained. The reaction time is 5 minutes to 12 hours, preferably 30 minutes to 4 hours, more preferably 30 minutes to 1 hour. .

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
In order to carry out more gently and efficiently, it is preferable to use a dehydrated and dried ether solvent or an aromatic hydrocarbon solvent.

  As a reaction atmosphere, it is preferable to carry out in nitrogen or argon atmosphere, More preferably, dry gas is used.

  Specific examples of the organometallic compound (B) ′ are shown below using a general formula.

(In each formula, X ₆ , R ₂ and R ₃ have the same meanings as described above.)
Examples of reaction formulas using general formulas relating to this step are shown below.

(In each formula, X ₆ , R ₂ and R ₃ have the same meanings as described above.)

Next, the second step will be described.
In the second step, the organometallic compound (B) ′ and the compound represented by the general formula (C) are cross-coupled in the presence of a transition metal salt or a transition metal complex, and represented by the general formula (D). This is a process for producing a compound to be produced.

Many of the compounds represented by formula (C) are commercially available and are easily available. The kind of halogen atom of X _{1 to} X _{4 in} this compound (C) is not particularly limited as long as it can be regioselectively reacted and may be the same or different, but preferably the reactivity of X ₁ and X ₂ Is preferably lower than the reactivity of each of X ₃ and X ₄ .
Therefore, as a preferable combination,
(X ₁ = X ₂ = F or Cl, X ₃ = X ₄ = Br or I),
An even more preferred combination is
(X ₁ = X ₂ = F, X ₃ = X ₄ = Br or I),
Particularly preferred combinations are:
(X ₁ = X ₂ = F, X ₃ = X ₄ = Br), (X ₁ = X ₂ = F, X ₃ = I, X ₄ = Br).

The molar ratio between the organometallic compound (B) ′ and the compound represented by the general formula (C) is not particularly limited as long as the compound (D) can be obtained, and is preferably 0.8 to 1.5. Is 0.9 to 1.2, more preferably 0.95 to 1.05.
In addition, (B) ′ can also be used without isolation in the first step. In that case, the molar ratio of the compound (B) to the compound (C) is particularly within the range where the compound (D) can be obtained. It is not restrict | limited, It is 0.8-1.5, Preferably it is 0.9-1.2, More preferably, it is 0.95-1.05.

The transition metal used in the reaction is a metal from Sc to Zn as the first transition element, Y to Cd as the second transition element, and La to Hg as the third transition element.
In the transition metal,
Iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold are preferred,
In order to improve the reactivity,
More preferably, nickel, molybdenum, ruthenium, rhodium, palladium, iridium, platinum, gold,
In order to further improve the reactivity, ruthenium, palladium, and platinum are particularly preferable.

As a transition metal salt or transition metal complex, the transition metal,
Water, hydrogen fluoride, hydrogen chloride, hydrobromic acid, hydrogen iodide, perchloric acid, nitric acid, sulfuric acid, phosphoric acid, fluorosulfuric acid, chlorosulfuric acid, tetrafluoroboric acid, hexafluorophosphoric acid, phosphotungstic acid, etc. Heteropoly acids, alkyl sulfonic acids, optionally halogenated alkyl sulfonic acids, aryl sulfonic acids, aryl sulfonic acids optionally having an alkyl side chain, phosphonic acids, carboxylic acids, optionally halogenated carboxylic acids Acidic compounds such as acids;
Ligands such as alkene, alkyne, amine, phosphine, arsine, N-heterocyclic carbene, dibenzylideneacetone, acetylacetone, carbon monoxide, nitrile, salen;
And salts or complexes thereof.

Illustrative examples of the further preferred transition metal salts or transition metal complexes are:
Tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis [1,2-bis (diphenylphosphino) ethane] palladium ( 0), bis (tri-t-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (0), bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2 , 4,6-trimethylphenyl) imidazol-2-ylidene] palladium (0), Palladium (II) oxide, palladium (II) nitrate, dichlorobenzyl bis (triphenylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), chloroallyl palladium (II) dimer, dichlorobis (acetonitrile) palladium ( II), dichlorobis (benzonitrile) palladium (II), bis (triphenylphosphine) palladium (II) acetate, bis (triphenylphosphine) palladium (II) trifluoroacetate, dichloro (cis, cis-1,5-cyclohexane) Octanediene) palladium (II), palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) pivalate, bis (trifluoromethanesulfonic acid) tetrakis (acetonitrile) para Um (II), acetylacetone palladium (II), palladium chloride (II), palladium bromide (II), sodium tetrachloropalladium (II), dichloro 2,5-norbornadiene palladium (II), nitric acid (ethylenediamine) palladium ( II), dichloro [9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene] palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), di-μ-chlorobis [5 -Hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium (II) dimer, dichloro [di-tert-butyl (chloro) phosphine] palladium (II) dimer, chloro [(tri-tert-butylphosphine) -2- (2-aminobiphenyl)] paradi (II), dichlorobis (tri-o-tolylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) imidazole-2- Iridene] palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) Imidazol-2-ylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), arylchloro [1,3-bis (2,4 , 6-Trimethylphenyl) imidazole- -Ilidene] palladium (II), arylchloro [1,3-bis (2,4,6-trimethylphenyl) 2-imidazolidinylidene] palladium (II), dichloro (di-μ-chloro) bis [1,3 -Bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II), palladium salts or complexes such as palladium / carbon, palladium / alumina, palladium / barium carbonate, palladium / barium sulfate;

cis-bis (2,2′-bipyridyl) dichlororuthenium (II) dihydrate, [(R) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl] ruthenium (II) dichloride , Carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (II), chloronitrosyl [N, N′-bis (3,5-di-tert-butylsalicylidene) -1,1,2,2-tetramethyl Ethylenediaminato] ruthenium (IV), chloro (pentamethylcyclopentadienyl) ruthenium (II) tetramer, dichloro (p-cymene) ruthenium (II) dimer, 1-hydroxytetraphenylcyclopentadienyl (tetraphenyl-2) , 4-cyclopentadien-1-one) -μ-hydrotetracarbonyldiruthenium (II), Ruthenium (III) bromide, chloro (p-cymene) ruthenium (II), chloronitrosylruthenium (II) monohydrate, triruthenium (0) dodecacarbonyl, tris (2,4-pentanedionato) ruthenium (III) , Ruthenium salts or complexes such as dichlorotris (triphenylphosphine) ruthenium (II), ruthenium / carbon,
Tetrakis (triphenylphosphine) platinum (0), bis (tri-tert-butylphosphine) platinum (0), platinum chloride (II), acetylacetone platinum (II), cis-diamine (1,1-cyclobutanedicarboxylate) Platinum salts or complexes such as platinum (II), dichloro cis-diammine platinum (II), dichloro (1,5-cyclooctadiene) platinum (II), (trans-1,2-cyclohexanediamine) oxalato platinum (II) Is mentioned.

  The transition metal salt or the transition metal complex can be used alone or in combination of two or more thereof, and the amount used thereof is not particularly limited as long as the compound (D) can be obtained. It is 0.001-10 equivalent, Preferably it is 0.005-1 equivalent, More preferably, it is 0.01-0.1 equivalent.

Furthermore, a ligand may be used in combination in order to promote the bond formation reaction.
Examples of the ligand include trimethylphosphine, triethylphosphine, tri-n-butyl) phosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, and di-tert-butylmethyl. Monodentate phosphine-based ligands such as phosphine; bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene, , 1'-bis bidentate phosphine ligand such as (diphenylphosphino) _{ferrocene; XPhos, tert-BuXPhos, Me4tert} -BuXPhos, SPhos, SPhos-SO 3 Na, MePhos, tert-BuMePhos, RuPhos, Bret Buchwald ligands such as Phos, JohnPhos, CyJohnPhos, DavePhos, PhDavePhos, tert-BuDavePhos; 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene, 1,3-bis (2,4,6 N-heterocyclic carbene (NHC) ligands such as -trimethylphenylphenyl) imidazol-2-ylidene.

  The ligand can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the compound (D) is obtained. For example, the transition metal salt or the transition metal complex 1 to 20 equivalents, preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents.

In order to promote the bond formation reaction, a base may be used in combination.
Examples of the base include carbonates such as sodium carbonate, potassium carbonate, cesium carbonate;
Phosphates such as sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate;
Hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide,
Fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride;
Alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide;
Trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza -Tertiary amines such as bicyclo [2.2.2] octane;
2,3-dimethylpyridine such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, t-butylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3, Pyridine derivatives such as 5-dimethylpyridine, 2-methyl-5-ethyl-pyridine, 2,6-diisopropylpyridine, 2,6-ditert-butylpyridine;
Are mentioned,

  Preferably, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, water Cesium oxide, potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza-bicyclo [2.2.2] octane,

More preferably, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, Cesium hydroxide,
Fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
Particularly preferably, sodium carbonate, potassium carbonate, cesium carbonate,
Sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, trimethylamine, triethylamine, tributylamine, diisopropylethylamine It is.

  The base can be used alone or in combination of two or more thereof, and the amount used thereof is not particularly limited as long as the compound (D) is obtained, and is 1 to 100 equivalents, preferably 1 with respect to the compound (C). -20 equivalents, more preferably 1-10 equivalents.

The reaction temperature is not particularly limited as long as the compound (D) is obtained, and is −80 to 200 ° C., preferably −20 to 100 ° C., but is regioselective with respect to the compound (C). In order to introduce only one thiophene ring, it is preferably 0 to 30 ° C.
The reaction time is not particularly limited as long as the compound (D) is obtained. The reaction time is 5 minutes to 120 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 12 hours.

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
In order to carry out more gently and efficiently, it is preferable to use a dehydrated and dried ether solvent or an aromatic hydrocarbon solvent.

  As a reaction atmosphere, it is preferable to carry out in nitrogen or argon atmosphere, More preferably, dry gas is used.

  The compound (D) obtained in the second step may be appropriately purified. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, recrystallization, size exclusion chromatography, sublimation purification, etc. are mentioned. When a by-product having two or more thiophene rings introduced into the benzene ring is produced, it is more preferable to completely remove these by-products in order to efficiently perform the subsequent steps.

Next, the third step will be described.
Third step, a compound represented by the general formula (E), is a step of converting the organometallic compound to X ₇ with the active site (E) '.

Many of the compounds represented by formula (E) are commercially available and are easily available. It can also be synthesized by the method described in Journal of Materials Chemistry, 2009, Vol. 19, pages 5913-5915. When the compound (E) is derived into an organometallic compound using X ₇ as a reaction point, a boron substituent, a silicon substituent, a tin substituent, a magnesium substituent, a zinc substituent used in a general cross-coupling reaction Etc. can be introduced. In order to efficiently perform the stepwise reaction under mild conditions, it is more preferable to perform the Negishi reaction using a zinc substituent.

Examples of the boron substituent that can be used include a boronyl group (B (OH) ₂ ), an ester derivative of a boronyl group, and a borabicyclo [3.3.1] nonanyl group (9-BBN). Examples of the silicon substituent include an arylsilyl group, a haloalkylsilyl group, and an alkoxysilyl group. Examples of the tin substituent include a trialkylstannyl group. Examples of the magnesium substituent include a magnesium fluoro group (MgF), a magnesium chloro group (MgCl), a magnesium bromo group (MgBr), and a magnesium iodo group (MgI). Examples of the zinc substituent include zinc fluoro group (ZnF), zinc chloro group (ZnCl), zinc bromo group (ZnBr), and zinc iodide group (ZnI).

  The molar ratio between the compound represented by the general formula (E) and various reactants for deriving the organometallic compound is not particularly limited as long as the compound (E) ′ is obtained. -2.0, preferably 0.9-1.2, more preferably 0.95-1.05.

The reaction temperature is not particularly limited as long as compound (E) ′ is obtained, and is −100 to 100 ° C., preferably −80 to 40 ° C.
The reaction time is not particularly limited as long as the compound (E) ′ is obtained. The reaction time is 5 minutes to 12 hours, preferably 30 minutes to 4 hours, and more preferably 30 minutes to 1 hour. .

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
In order to carry out more gently and efficiently, it is preferable to use a dehydrated and dried ether solvent or an aromatic hydrocarbon solvent.

  As a reaction atmosphere, it is preferable to carry out in nitrogen or argon atmosphere, More preferably, dry gas is used.

  Specific examples of the organometallic compound (E) ′ are shown below using a general formula.

(In each formula, X ₈ , R ₇ and R ₈ have the same meanings as described above.)
Examples of reaction formulas using general formulas relating to this step are shown below.

(In each formula, X ₈ , R ₇ and R ₈ have the same meanings as described above.)
Next, the fourth step will be described.
In the fourth step, the organometallic compound (E) ′ and the compound represented by the general formula (D) are cross-coupled in the presence of a transition metal salt or a transition metal complex, and the general formula (F) It is a process for producing the represented compound.

The transition metal used in the reaction is a metal from Sc to Zn as the first transition element, Y to Cd as the second transition element, and La to Hg as the third transition element.
In the transition metal,
Iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold are preferred,
In order to improve the reactivity,
More preferably, nickel, molybdenum, ruthenium, rhodium, palladium, iridium, platinum, gold,
In order to further improve the reactivity, ruthenium, palladium, and platinum are particularly preferable.

As a transition metal salt or transition metal complex, the transition metal,
Water, hydrogen fluoride, hydrogen chloride, hydrobromic acid, hydrogen iodide, perchloric acid, nitric acid, sulfuric acid, phosphoric acid, fluorosulfuric acid, chlorosulfuric acid, tetrafluoroboric acid, hexafluorophosphoric acid, phosphotungstic acid, etc. Heteropoly acids, alkyl sulfonic acids, optionally halogenated alkyl sulfonic acids, aryl sulfonic acids, aryl sulfonic acids optionally having an alkyl side chain, phosphonic acids, carboxylic acids, optionally halogenated carboxylic acids Acidic compounds such as acids;
Ligands such as alkene, alkyne, amine, phosphine, arsine, N-heterocyclic carbene, dibenzylideneacetone, acetylacetone, carbon monoxide, nitrile, salen;
And salts or complexes thereof.

Illustrative examples of the further preferred transition metal salts or transition metal complexes are:
Tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis [1,2-bis (diphenylphosphino) ethane] palladium ( 0), bis (tri-t-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (0), bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2 , 4,6-trimethylphenyl) imidazol-2-ylidene] palladium (0), Palladium (II) oxide, palladium (II) nitrate, dichlorobenzyl bis (triphenylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), chloroallyl palladium (II) dimer, dichlorobis (acetonitrile) palladium ( II), dichlorobis (benzonitrile) palladium (II), bis (triphenylphosphine) palladium (II) acetate, bis (triphenylphosphine) palladium (II) trifluoroacetate, dichloro (cis, cis-1,5-cyclohexane) Octanediene) palladium (II), palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) pivalate, bis (trifluoromethanesulfonic acid) tetrakis (acetonitrile) para Um (II), acetylacetone palladium (II), palladium chloride (II), palladium bromide (II), sodium tetrachloropalladium (II), dichloro 2,5-norbornadiene palladium (II), nitric acid (ethylenediamine) palladium ( II), dichloro [9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene] palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), di-μ-chlorobis [5 -Hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium (II) dimer, dichloro [di-tert-butyl (chloro) phosphine] palladium (II) dimer, chloro [(tri-tert-butylphosphine) -2- (2-aminobiphenyl)] paradi (II), dichlorobis (tri-o-tolylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) imidazole-2- Iridene] palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) Imidazol-2-ylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), arylchloro [1,3-bis (2,4 , 6-Trimethylphenyl) imidazole- -Ilidene] palladium (II), arylchloro [1,3-bis (2,4,6-trimethylphenyl) 2-imidazolidinylidene] palladium (II), dichloro (di-μ-chloro) bis [1,3 -Bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II), palladium salts or complexes such as palladium / carbon, palladium / alumina, palladium / barium carbonate, palladium / barium sulfate;

cis-bis (2,2′-bipyridyl) dichlororuthenium (II) dihydrate, [(R) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl] ruthenium (II) dichloride , Carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (II), chloronitrosyl [N, N′-bis (3,5-di-tert-butylsalicylidene) -1,1,2,2-tetramethyl Ethylenediaminato] ruthenium (IV), chloro (pentamethylcyclopentadienyl) ruthenium (II) tetramer, dichloro (p-cymene) ruthenium (II) dimer, 1-hydroxytetraphenylcyclopentadienyl (tetraphenyl-2) , 4-cyclopentadien-1-one) -μ-hydrotetracarbonyldiruthenium (II), Ruthenium (III) bromide, chloro (p-cymene) ruthenium (II), chloronitrosylruthenium (II) monohydrate, triruthenium (0) dodecacarbonyl, tris (2,4-pentanedionato) ruthenium (III) , Ruthenium salts or complexes such as dichlorotris (triphenylphosphine) ruthenium (II), ruthenium / carbon,
Tetrakis (triphenylphosphine) platinum (0), bis (tri-tert-butylphosphine) platinum (0), platinum chloride (II), acetylacetone platinum (II), cis-diamine (1,1-cyclobutanedicarboxylate) Platinum salts or complexes such as platinum (II), dichloro cis-diammine platinum (II), dichloro (1,5-cyclooctadiene) platinum (II), (trans-1,2-cyclohexanediamine) oxalato platinum (II) Is mentioned.

  The transition metal salt or the transition metal complex can be used alone or in combination of two or more thereof, and the amount used thereof is not particularly limited as long as the compound (F) can be obtained. It is 0.001-10 equivalent, Preferably it is 0.005-1 equivalent, More preferably, it is 0.01-0.03 equivalent.

Furthermore, a ligand may be used in combination in order to promote the bond formation reaction.
Examples of the ligand include trimethylphosphine, triethylphosphine, tri-n-butyl) phosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, and di-tert-butylmethyl. Monodentate phosphine-based ligands such as phosphine; bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene, , 1'-bis bidentate phosphine ligand such as (diphenylphosphino) _{ferrocene; XPhos, tert-BuXPhos, Me4tert} -BuXPhos, SPhos, SPhos-SO 3 Na, MePhos, tert-BuMePhos, RuPhos, Bret Buchwald ligands such as Phos, JohnPhos, CyJohnPhos, DavePhos, PhDavePhos, tert-BuDavePhos; 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene, 1,3-bis (2,4,6 N-heterocyclic carbene (NHC) ligands such as -trimethylphenylphenyl) imidazol-2-ylidene and the like.

  The ligands can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the compound (F) is obtained. For example, the transition metal salt or the transition metal complex 1 to 20 equivalents, preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents.

In order to promote the bond formation reaction, a base may be used in combination.
Examples of the base include carbonates such as sodium carbonate, potassium carbonate, cesium carbonate;
Phosphates such as sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate;
Hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide,
Fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride;
Alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide;
Trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza -Tertiary amines such as bicyclo [2.2.2] octane;
2,3-dimethylpyridine such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, t-butylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3, Pyridine derivatives such as 5-dimethylpyridine, 2-methyl-5-ethyl-pyridine, 2,6-diisopropylpyridine, 2,6-ditert-butylpyridine;
Are mentioned,

  Preferably, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, water Cesium oxide, potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza-bicyclo [2.2.2] octane,

More preferably, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, Cesium hydroxide,
Fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
Particularly preferably, sodium carbonate, potassium carbonate, cesium carbonate,
Sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, trimethylamine, triethylamine, tributylamine, diisopropylethylamine It is.

  The bases can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the compound (F) can be obtained, and is 1 to 100 equivalents, preferably 1 with respect to the compound (D). -20 equivalents, more preferably 1-10 equivalents.

  The reaction temperature is not particularly limited as long as the compound (F) can be obtained, and is −80 to 200 ° C., preferably 0 to 100 ° C., more preferably 30 to 70 ° C.

  The reaction time is not particularly limited as long as the compound (F) is obtained. The reaction time is 5 minutes to 120 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 12 hours.

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
In order to carry out more gently and efficiently, it is preferable to use a dehydrated and dried ether solvent or an aromatic hydrocarbon solvent.
As a reaction atmosphere, it is preferable to carry out in nitrogen or argon atmosphere, More preferably, dry gas is used.

  The compound (F) obtained in the fourth step is preferably purified in order to efficiently perform the subsequent steps. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, recrystallization, size exclusion chromatography, sublimation purification, etc. are mentioned.

Finally, the compound represented by the general formula (F) is converted into a compound represented by the general formula (A). This step may be any step as long as the compound represented by the general formula (F) can be converted into the compound represented by the general formula (A).
For example, a step of “producing a compound represented by the general formula (A) by carrying out a crosslinking reaction of the compound represented by the general formula (F) in the presence of an alkali metal sulfide” can be mentioned.

  Examples of alkali metal sulfides that can be used include sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and hydrates thereof. In order to carry out more efficiently, it is preferable to use sodium sulfide nonahydrate.

The salt can be used alone or in combination of two or more, and the amount used thereof is not particularly limited as long as the compound (A) is obtained, and is preferably 1.5 to 10 equivalents relative to the compound (F). Is 2 to 5 equivalents, more preferably 2.0 to 2.2 equivalents.

The reaction temperature is not particularly limited as long as the compound (A) can be obtained, and is 0 to 250 ° C, preferably 50 to 200 ° C, more preferably 150 to 180 ° C.
The reaction time is not particularly limited as long as the compound (A) is obtained. The reaction time is 5 minutes to 12 hours, preferably 30 minutes to 4 hours, and more preferably 1 to 3 hours.

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
In order to carry out more efficiently, it is preferable to use an amide solvent having a high boiling point.

  Although the reaction atmosphere can be carried out under air, it is preferably carried out in a nitrogen or argon atmosphere in order to prevent oxidation reaction during high temperature stirring.

  The obtained compound (A) may be appropriately purified. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, recrystallization, size exclusion chromatography, sublimation purification, etc. are mentioned.

<Production method 2 of the present invention>
The production method of the present invention comprises:
It is a manufacturing method of the dithienobenzodithiophene derivative represented by general formula (G), Comprising: It has the manufacturing process as described in the following (I)-(III).
(I) a first step of producing a compound represented by the general formula (I) by monohalogenating a compound represented by the general formula (H) in the presence of N-halosuccinimide (NXS);
(II) A compound represented by general formula (I) and a compound represented by general formula (J) or general formula (K) are subjected to a cross-coupling reaction in the presence of a transition metal catalyst, A second step for producing the compound represented,
(III) The compound represented by the general formula (L) is subjected to catalytic hydrogen reduction in the presence of a heterogeneous transition metal catalyst or a homogeneous transition metal catalyst to obtain a dithienobenzodithiophene derivative represented by the general formula (G). Third process to manufacture.

(In each formula, R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ represent a hydrogen atom or an arbitrary substituent, X ₁₁ represents a halogen atom, and Y ₁₁ − represents CH ₃ — (CH ₂ ) _n−2 −. C≡C— or CH ₃ — (CH ₂ ) _n−2 —CH═CH—, where n represents an integer of 2 to 19.

The substituents R ₁₀₃ , R ₁₀₅ , R ₁₀₈ , and R ₁₁₀ of the compounds represented by the general formulas (G) to (L) related to the production method of the present invention are each independently substituted as a substituent of the aromatic compound. A well-known and commonly used substituent (however, an inert substituent that does not become a reaction active part in the production process described later) can be used. As a specific example,
A hydrogen atom (including light hydrogen, deuterium and tritium),
An acyclic or cyclic alkyl group having 1 to 20 carbon atoms (in which —CH ₂ — in the alkyl group is —O—, —CO, so that an oxygen atom, a sulfur atom and a nitrogen atom are not directly bonded to each other); -, - OCO -, - COO -, - S -, - SO 2 -, - SO -, - NH-, or -NR'- may be substituted with a hydrogen atom in the alkyl group, an aromatic group , A halogeno group, or a nitrile group (wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms), a halogeno group, an aromatic group (the aromatic group) The group may be substituted with an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, a halogeno group, an aromatic group, or a nitrile group, and —CH ₂ — in the alkyl group is -O-,-so that the oxygen atom, sulfur atom and nitrogen atom are not directly bonded to each other. O -, - OCO -, - COO -, - S -, - SO 2 -, - SO -, - NH-, or -NR '' - may be substituted with a hydrogen atom in the alkyl group, aromatic Group, halogeno group, or nitrile group (where R ″ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms)), a nitro group, or a nitrile group However, it is not limited to these.

Among these substituents,
Preferably,
A hydrogen atom, an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, a fluoro (F) group, an aromatic group, a nitro group, or a nitrile group,
More preferably,
A hydrogen atom, an acyclic or cyclic alkyl group having 1 to 20 carbon atoms, more preferably,
It is a hydrogen atom or an acyclic alkyl group having 1 to 20 carbon atoms.

Specific examples of the acyclic alkyl group having 1 to 20 carbon atoms include
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 1-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-trimethylhexyl group, n-decyl group, n-undecyl Group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- eicosyl group and the like.

Next, the effect of this manufacturing method will be described.
As shown in the reaction formula (1), a known and commonly used method for producing a dithienobenzodithiophene derivative (JP-A-2014-22498) has two positions at the 2-position and 7-position (in the α-position of the thiophene ring) of dithienobenzodithiophene. This is a technique in which a Friedel-Crafts reaction is performed using both hydrogen atoms as reaction points, and the same substituent is simultaneously introduced into these two reaction points.

Therefore, in this method, a compound represented by the general formula (G) cannot be produced. On the other hand, in this production method, a halogen atom is once introduced using one of the two hydrogen atoms at the 2-position and the 7-position of the dithienobenzodithiophene derivative represented by the general formula (H) as a reaction point. In this method, the activity at one reaction point is increased, and different substituents can be introduced stepwise and regioselectively in subsequent reactions. The compound represented by the general formula (G) is the same as the compound represented by the general formula (A) with respect to “R ₂ , R ₃ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₂ and R ₇ are the same. Or, R ₃ and R ₈ are the same or different, R ₅ and R ₁₀ are the same, and at least one of the two combinations of R ₂ and R ₇ , R ₃ and R ₈ is different from each other Therefore, as described above, since such a derivative has broken symmetry, it has excellent solvent solubility, and thus has suitability as an organic semiconductor ink, Furthermore, since the cohesiveness is controlled, it is possible to achieve high semiconductor characteristics (mobility) with a simple and practical wet film formation method (ie, a method of “dropping ink droplets and drying them”). ) Organic semiconductor film can be given .

  First, the first step will be described.

  In the first step, the compound represented by the general formula (H) is monohalogenated in the presence of N-halosuccinimide (NXS) to produce the compound represented by the general formula (I).

The compound represented by the general formula (H) is the above-mentioned “Production Method 1 of the Present Invention” (where R ₂ = H, R ₃ = R ₁₀₃ , R ₅ = R ₁₀₅ , R ₇ = H, R ₈ = R). ₁₀₈ , R ₁₀ = R ₁₁₀ )).
The amount of NXS used (molar ratio) to the compound represented by the general formula (H) is usually 0.80 to 1.20, preferably 0.90 to 1.10, more preferably 0.95 to 1. .05.
Examples of N-halosuccinimide (NXS) used in the reaction include N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), and N-iodosuccinimide (NIS).

  In order to facilitate removal of by-products into which two halogen atoms have been introduced, due to the difference in solubility, N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), etc. are used to make more disubstituted by-products. It is preferable to introduce a heavy atom that tends to lower the solubility of the organism.

In order to introduce the substituents in the subsequent stages under milder and simpler conditions, heavy atoms with higher elimination ability are introduced using N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), etc. It is preferable to do.
Therefore, among NXS, NBS and NIS are preferable.

In order to improve the reactivity in the subsequent steps and the separation ability from disubstituted byproducts, the introduced halogen atom can be changed to a more polar leaving group. Further, it can be changed to a boron, tin, silicon, zinc, magnesium functional group or the like used for general cross coupling.
Examples of more polar leaving groups include sulfonate ester substituents such as mesylate and tosylate.

The reaction temperature is not particularly limited as long as compound (I) is obtained, and is −80 to 200 ° C., preferably −20 to 100 ° C., and more preferably 25 to 60 ° C.
The reaction time is not particularly limited as long as Compound (I) is obtained, and is 5 minutes to 120 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 2 hours.

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as benzene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
In order to carry out milder and more efficiently, it is preferable to use a halogen-based solvent or an aliphatic hydrocarbon solvent that has been dehydrated and dried.

The reaction atmosphere can be carried out in air, but is preferably carried out in a dry nitrogen or dry argon atmosphere.
Compound (I) obtained in the first step may be appropriately purified. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, size exclusion chromatography, recrystallization, sublimation purification, etc. are mentioned.

Next, the second step will be described.
In the second step, the compound represented by the general formula (J) or the general formula (K) in the presence of a transition metal salt or a transition metal complex is cross-linked to the compound represented by the general formula (I). Ringing to produce a compound represented by the general formula (L).

The transition metal used in the reaction is a metal from Sc to Zn as the first transition element, Y to Cd as the second transition element, and La to Hg as the third transition element.
In the transition metal,
Iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold are preferred,
In order to improve the reactivity,
More preferably, nickel, molybdenum, ruthenium, rhodium, palladium, iridium, platinum, gold,
In order to further improve the reactivity, ruthenium, palladium, and platinum are particularly preferable.

As a transition metal salt or transition metal complex, the transition metal,
Water, hydrogen fluoride, hydrogen chloride, hydrobromic acid, hydrogen iodide, perchloric acid, nitric acid, sulfuric acid, phosphoric acid, fluorosulfuric acid, chlorosulfuric acid, tetrafluoroboric acid, hexafluorophosphoric acid, phosphotungstic acid, etc. Heteropoly acids, alkyl sulfonic acids, optionally halogenated alkyl sulfonic acids, aryl sulfonic acids, aryl sulfonic acids optionally having an alkyl side chain, phosphonic acids, carboxylic acids, optionally halogenated carboxylic acids Acidic compounds such as acids;
Ligands such as alkene, alkyne, amine, phosphine, arsine, N-heterocyclic carbene, dibenzylideneacetone, acetylacetone, carbon monoxide, nitrile, salen;
And salts or complexes thereof.

Illustrative examples of the further preferred transition metal salts or transition metal complexes are:
Tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis [1,2-bis (diphenylphosphino) ethane] palladium ( 0), bis (tri-t-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (0), bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2 , 4,6-trimethylphenyl) imidazol-2-ylidene] palladium (0), Palladium (II) oxide, palladium (II) nitrate, dichlorobenzyl bis (triphenylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), chloroallyl palladium (II) dimer, dichlorobis (acetonitrile) palladium ( II), dichlorobis (benzonitrile) palladium (II), bis (triphenylphosphine) palladium (II) acetate, bis (triphenylphosphine) palladium (II) trifluoroacetate, dichloro (cis, cis-1,5-cyclohexane) Octanediene) palladium (II), palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) pivalate, bis (trifluoromethanesulfonic acid) tetrakis (acetonitrile) para Um (II), acetylacetone palladium (II), palladium chloride (II), palladium bromide (II), sodium tetrachloropalladium (II), dichloro 2,5-norbornadiene palladium (II), nitric acid (ethylenediamine) palladium ( II), dichloro [9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene] palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), di-μ-chlorobis [5 -Hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium (II) dimer, dichloro [di-tert-butyl (chloro) phosphine] palladium (II) dimer, chloro [(tri-tert-butylphosphine) -2- (2-aminobiphenyl)] paradi (II), dichlorobis (tri-o-tolylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) imidazole-2- Iridene] palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) Imidazol-2-ylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), arylchloro [1,3-bis (2,4 , 6-Trimethylphenyl) imidazole- -Ilidene] palladium (II), arylchloro [1,3-bis (2,4,6-trimethylphenyl) 2-imidazolidinylidene] palladium (II), dichloro (di-μ-chloro) bis [1,3 -Bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II), palladium salts or complexes such as palladium / carbon, palladium / alumina, palladium / barium carbonate, palladium / barium sulfate;

cis-bis (2,2′-bipyridyl) dichlororuthenium (II) dihydrate, [(R) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl] ruthenium (II) dichloride , Carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (II), chloronitrosyl [N, N′-bis (3,5-di-tert-butylsalicylidene) -1,1,2,2-tetramethyl Ethylenediaminato] ruthenium (IV), chloro (pentamethylcyclopentadienyl) ruthenium (II) tetramer, dichloro (p-cymene) ruthenium (II) dimer, 1-hydroxytetraphenylcyclopentadienyl (tetraphenyl-2) , 4-cyclopentadien-1-one) -μ-hydrotetracarbonyldiruthenium (II), Ruthenium (III) bromide, chloro (p-cymene) ruthenium (II), chloronitrosylruthenium (II) monohydrate, triruthenium (0) dodecacarbonyl, tris (2,4-pentanedionato) ruthenium (III) , Ruthenium salts or complexes such as dichlorotris (triphenylphosphine) ruthenium (II), ruthenium / carbon,
Tetrakis (triphenylphosphine) platinum (0), bis (tri-tert-butylphosphine) platinum (0), platinum chloride (II), acetylacetone platinum (II), cis-diamine (1,1-cyclobutanedicarboxylate) Platinum salts or complexes such as platinum (II), dichloro cis-diammine platinum (II), dichloro (1,5-cyclooctadiene) platinum (II), (trans-1,2-cyclohexanediamine) oxalato platinum (II) Is mentioned.

  The transition metal salt or transition metal complex can be used alone or in combination of two or more thereof, and the amount used is not particularly limited as long as the compound (L) is obtained, and is 0 with respect to (I). 0.001 to 10 equivalents, preferably 0.005 to 5 equivalents, more preferably 0.01 to 0.1 equivalents.

Furthermore, a ligand may be used in combination in order to promote the bond formation reaction.
Examples of the ligand include trimethylphosphine, triethylphosphine, tri-n-butyl) phosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, and di-tert-butylmethyl. Monodentate phosphine-based ligands such as phosphine; bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene, , 1'-bis bidentate phosphine ligand such as (diphenylphosphino) _{ferrocene; XPhos, tert-BuXPhos, Me4tert} -BuXPhos, SPhos, SPhos-SO 3 Na, MePhos, tert-BuMePhos, RuPhos, Bret Buchwald ligands such as Phos, JohnPhos, CyJohnPhos, DavePhos, PhDavePhos, tert-BuDavePhos; 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene, 1,3-bis (2,4,6 N-heterocyclic carbene (NHC) ligands such as -trimethylphenylphenyl) imidazol-2-ylidene.

  The ligand can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the compound (L) can be obtained. For example, the transition metal salt or the transition metal complex 1 to 20 equivalents, preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents.

In order to promote the bond formation reaction, a base may be used in combination.
Examples of the base include carbonates such as sodium carbonate, potassium carbonate, cesium carbonate;
Phosphates such as sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate;
Hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide,
Fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride;
Alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide;
Trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza -Tertiary amines such as bicyclo [2.2.2] octane;
2,3-dimethylpyridine such as pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, t-butylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3, Pyridine derivatives such as 5-dimethylpyridine, 2-methyl-5-ethyl-pyridine, 2,6-diisopropylpyridine, 2,6-ditert-butylpyridine;
Are mentioned,

  Preferably, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, water Cesium oxide, potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,4-diaza-bicyclo [2.2.2] octane,

More preferably, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, Cesium hydroxide,
Fluorides such as potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
Particularly preferably, sodium carbonate, potassium carbonate, cesium carbonate,
Sodium phosphate, disodium phosphate, trisodium phosphate, potassium phosphate, calcium phosphate, diammonium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, trimethylamine, triethylamine, tributylamine, diisopropylethylamine It is.

  The bases can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the compound (L) is obtained, and is 1 to 100 equivalents, preferably 1 with respect to the raw material (I). -20 equivalents, more preferably 1-10 equivalents.

The reaction temperature is not particularly limited as long as the compound (L) can be obtained, and is −80 to 200 ° C., preferably −20 to 100 ° C., more preferably 25 to 60 ° C.
The reaction time is not particularly limited as long as the compound (L) is obtained, and is 5 minutes to 120 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 2 hours.

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
These solvents can be used alone or in combination of two or more.
For more mild and efficient use, it is preferable to use a dehydrated and dried ether solvent or amide solvent.

  The reaction atmosphere can be carried out in air, but is preferably carried out in a dry nitrogen or dry argon atmosphere.

  The compound (L) obtained in the second step is preferably purified in order to efficiently carry out the subsequent steps. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, recrystallization, size exclusion chromatography, sublimation purification, etc. are mentioned.

Next, the third step will be described.
In the third step, the compound represented by the general formula (L) is reduced to produce the compound represented by the general formula (G).
As the reduction method, a catalytic hydrogenation method using a heterogeneous transition metal catalyst or a catalytic hydrogenation method using a salt or complex of a homogeneous transition metal catalyst can be used. In order to carry out under mild conditions and facilitate post-treatment, a catalytic hydrogenation method using a heterogeneous catalyst is more preferable.

The transition metals used in the heterogeneous and homogeneous catalytic hydrogenation methods are Sc to Zn as the first transition element, Y to Cd as the second transition element, and La to Hg as the third transition element. Up to metal.
In the transition metal,
Nickel, copper, ruthenium, chromium, rhodium, palladium, osmium, iridium, platinum are preferred,
In order to improve the reactivity,
Particularly preferred are ruthenium, palladium and platinum.

When performed in a heterogeneous system, in the presence of hydrogen gas, the transition metal may be used together with an insoluble substance such as activated carbon or alumina as a carrier, or an activated transition metal having a large surface area may be used alone. The hydroxide or oxide may be reduced with hydrogen gas.
When performed in a homogeneous system, the transition metal salt or transition metal complex is used in the presence of hydrogen gas.

As a transition metal salt or transition metal complex, the transition metal,
Water, hydrogen fluoride, hydrogen chloride, hydrobromic acid, hydrogen iodide, perchloric acid, nitric acid, sulfuric acid, phosphoric acid, fluorosulfuric acid, chlorosulfuric acid, tetrafluoroboric acid, hexafluorophosphoric acid, phosphotungstic acid, etc. Heteropoly acids, alkyl sulfonic acids, optionally halogenated alkyl sulfonic acids, aryl sulfonic acids, aryl sulfonic acids optionally having an alkyl side chain, phosphonic acids, carboxylic acids, optionally halogenated carboxylic acids Acidic compounds such as acids;
Ligands such as alkene, alkyne, amine, phosphine, arsine, N-heterocyclic carbene, dibenzylideneacetone, acetylacetone, carbon monoxide, nitrile, salen;
And salts or complexes thereof.

Illustrative examples of the further preferred transition metal salts or transition metal complexes are:
Tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis [1,2-bis (diphenylphosphino) ethane] palladium ( 0), bis (tri-t-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (0), bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (0), bis (1,4-naphthoquinone) bis [1,3-bis (2 , 4,6-trimethylphenyl) imidazol-2-ylidene] palladium (0), Palladium (II) oxide, palladium (II) nitrate, dichlorobenzyl bis (triphenylphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), chloroallyl palladium (II) dimer, dichlorobis (acetonitrile) palladium ( II), dichlorobis (benzonitrile) palladium (II), bis (triphenylphosphine) palladium (II) acetate, bis (triphenylphosphine) palladium (II) trifluoroacetate, dichloro (cis, cis-1,5-cyclohexane) Octanediene) palladium (II), palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) pivalate, bis (trifluoromethanesulfonic acid) tetrakis (acetonitrile) para Um (II), acetylacetone palladium (II), palladium chloride (II), palladium bromide (II), sodium tetrachloropalladium (II), dichloro 2,5-norbornadiene palladium (II), nitric acid (ethylenediamine) palladium ( II), dichloro [9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene] palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), di-μ-chlorobis [5 -Hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium (II) dimer, dichloro [di-tert-butyl (chloro) phosphine] palladium (II) dimer, chloro [(tri-tert-butylphosphine) -2- (2-aminobiphenyl)] paradi (II), dichlorobis (tri-o-tolylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) imidazole-2- Iridene] palladium (II), arylchloro [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) Imidazol-2-ylidene] palladium (II), chlorophenylaryl [1,3-bis (2,6-diisopropylphenyl) 2-imidazolidinylidene] palladium (II), arylchloro [1,3-bis (2,4 , 6-Trimethylphenyl) imidazole- -Ilidene] palladium (II), arylchloro [1,3-bis (2,4,6-trimethylphenyl) 2-imidazolidinylidene] palladium (II), dichloro (di-μ-chloro) bis [1,3 -Bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II), palladium salts or complexes such as palladium / carbon, palladium / alumina, palladium / barium carbonate, palladium / barium sulfate;

cis-bis (2,2′-bipyridyl) dichlororuthenium (II) dihydrate, [(R) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl] ruthenium (II) dichloride , Carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (II), chloronitrosyl [N, N′-bis (3,5-di-tert-butylsalicylidene) -1,1,2,2-tetramethyl Ethylenediaminato] ruthenium (IV), chloro (pentamethylcyclopentadienyl) ruthenium (II) tetramer, dichloro (p-cymene) ruthenium (II) dimer, 1-hydroxytetraphenylcyclopentadienyl (tetraphenyl-2) , 4-cyclopentadien-1-one) -μ-hydrotetracarbonyldiruthenium (II), Ruthenium (III) bromide, chloro (p-cymene) ruthenium (II), chloronitrosylruthenium (II) monohydrate, triruthenium (0) dodecacarbonyl, tris (2,4-pentanedionato) ruthenium (III) , Ruthenium salts or complexes such as dichlorotris (triphenylphosphine) ruthenium (II), ruthenium / carbon,
Tetrakis (triphenylphosphine) platinum (0), bis (tri-tert-butylphosphine) platinum (0), platinum chloride (II), acetylacetone platinum (II), cis-diamine (1,1-cyclobutanedicarboxylate) Platinum salts or complexes such as platinum (II), dichloro cis-diammine platinum (II), dichloro (1,5-cyclooctadiene) platinum (II), (trans-1,2-cyclohexanediamine) oxalato platinum (II) Is mentioned.

  The transition metal salt or the transition metal complex can be used alone or in combination of two or more thereof, and the amount used thereof is not particularly limited as long as the compound (G) can be obtained. 0.001 to 10 equivalents, preferably 0.005 to 5 equivalents, more preferably 0.01 to 0.05 equivalents.

Furthermore, a ligand may be used in combination to promote the reduction reaction.
Examples of the ligand include trimethylphosphine, triethylphosphine, tri-n-butyl) phosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (o-tolyl) phosphine, and di-tert-butylmethyl. Monodentate phosphine-based ligands such as phosphine; bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene, , 1'-bis bidentate phosphine ligand such as (diphenylphosphino) _{ferrocene; XPhos, tert-BuXPhos, Me4tert} -BuXPhos, SPhos, SPhos-SO 3 Na, MePhos, tert-BuMePhos, RuPhos, Bret Buchwald ligands such as Phos, JohnPhos, CyJohnPhos, DavePhos, PhDavePhos, tert-BuDavePhos; 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene, 1,3-bis (2,4,6 N-heterocyclic carbene (NHC) ligands such as -trimethylphenylphenyl) imidazol-2-ylidene.

  The ligand can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the compound (G) can be obtained. For example, the transition metal salt or the transition metal complex 1 to 20 equivalents, preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents.

The reaction temperature is not particularly limited as long as the compound (G) can be obtained, and is −80 to 200 ° C., preferably −20 to 100 ° C., and more preferably 0 to 30 ° C.
The reaction time is not particularly limited as long as the compound (G) is obtained. The reaction time is 5 minutes to 240 hours, preferably 30 minutes to 24 hours, and more preferably 3 hours to 6 hours.

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;
Ester solvents such as ethyl acetate, isopropyl acetate, amyl acetate;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrodinone;
Sulfur-containing solvents such as dimethyl sulfoxide and sulfolane;
Nitrile solvents such as acetonitrile, valeronitrile, benzonitrile;
Carboxylic acid solvents such as acetic acid, propionic acid, butyric acid;
Alcohol solvents such as methanol, ethanol, propanol, butyl alcohol,
These solvents can be used alone or in combination of two or more.
For more mild and efficient use, it is preferable to use a dehydrated and dried ether solvent or alcohol solvent.

  As the reaction atmosphere, in the case of catalytic hydrogen reduction, it can be carried out in an air-hydrogen mixture, but it is preferably carried out in a nitrogen-hydrogen mixture or argon-hydrogen mixture atmosphere, more preferably in a dry hydrogen gas atmosphere. To do.

  The compound (G) obtained in the third step may be appropriately purified. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, recrystallization, size exclusion chromatography, sublimation purification, etc. are mentioned.

<Production method (3) of the present invention>
Next, the manufacturing method (3) of the present invention will be described.
The production method (3) of the present invention comprises:
A dithienobenzodithiophene derivative represented by the general formula (M) is prepared by reacting a dithienobenzodithiophene derivative represented by the general formula (G) ′ with an alkyl halide represented by the general formula (m) in the presence of organolithium. Is a method for producing a dithienobenzodithiophene derivative represented by the general formula (M).

(In each formula, R ₁₀₂ represents an alkyl group having 1 to 20 carbon atoms, R ₁₀₇ represents an alkyl group having 1 to 20 carbon atoms, and R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ are hydrogen atoms or Represents an arbitrary substituent, and X ₁₂ represents a halogen atom, provided that R ₁₀₂ and R ₁₀₇ are different.

The substituents R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ of the compounds represented by the general formula (G) ′ and the general formula (M) related to the production method of the present invention are the same as R ₁₀₃ described in the production method (2). , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ .
Specific examples of the alkyl group having 1 to 20 carbon atoms include
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 1-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-trimethylhexyl group, n-decyl group, n-undecyl Group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- eicosyl group and the like.

The dithienobenzodithiophene derivative represented by the general formula (G) ′ is “the production method 1 of the present invention” (provided that R ₂ = R ₁₀₂ , R ₃ = R ₁₀₃ , R ₅ = R ₁₀₅ , R ₇ = H, R ₈ = R ₁₀₈ and R ₁₀ = R ₁₁₀ ) or “Manufacturing method 2 of the present invention” (provided that CH ₃ — (CH ₂ ) n − is R ₁₀₂ ).

Examples of the organic lithium include alkyl lithium, aryl lithium, lithium diisopropylamide, and the like, and more preferably normal butyl lithium. As the general formula X ₁₂ alkyl halide represented by (m), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, more preferably an iodine atom.

  The use amount (molar ratio) of organolithium to the compound represented by the general formula (G) ′ is usually 0.80 to 2.00, preferably 0.90 to 1.10, more preferably 0.95. ~ 1.05. Moreover, the usage-amount (molar ratio) of the alkyl halide is 0.80-10.00 normally, Preferably it is 0.90-5.00, More preferably, it is 0.95-1.05.

  The reaction temperature at which the organic lithium is reacted is not particularly limited as long as the compound represented by the general formula (G) ′ is lithiated, and is −196 to 100 ° C., preferably −100 to 0 ° C. And more preferably from −78 to −60 ° C. The reaction temperature in the subsequent reaction with the alkyl halide is not particularly limited as long as the compound represented by the general formula (M) is obtained, and is −196 to 100 ° C., preferably −78. It is -30 degreeC, More preferably, it is 0-25 degreeC.

  The reaction time is not particularly limited as long as the compound represented by the general formula (M) is obtained. The time for reacting the organic lithium and the time for the subsequent reaction with the organic halogen reagent are 5 minutes to 10 minutes, respectively. Time, preferably 5 minutes to 4 hours, more preferably 15 minutes to 1 hour.

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;
aliphatic hydrocarbon solvents such as n-hexane, heptane, octane, cyclohexane, cyclopentane;
Aromatic hydrocarbon solvents such as toluene, benzene, xylene;
These solvents can be used alone or in combination of two or more.
In order to carry out more efficiently, it is preferable to use a dehydrated ether solvent.

  The reaction atmosphere can be carried out in dry air, but it is preferably carried out in a dry nitrogen or dry argon atmosphere for efficiency.

  The compound (M) obtained by the production method (3) may be appropriately purified. Although it does not specifically limit as a purification method, For example, normal phase and reverse phase column chromatography, size exclusion chromatography, recrystallization, sublimation purification, etc. are mentioned.

(Dithienobenzodithiophene derivative of the present invention)
Hereinafter, the dithienobenzodithiophene derivative of the present invention will be described.
The dithienobenzodithiophene derivative of the present invention is a dithienobenzodithiophene derivative represented by the general formula (N).

(In the formula, R ₂₂ represents a linear alkyl group having 2 to 20 carbon atoms, and R ₂₇ represents a hydrogen atom or a methyl group.)

A feature of the compound of the present invention is that substituents having different alkyl chain lengths are introduced into the substituents R ₂₂ and R ₂₇ . When R ₂₂ and R ₂₇ are the same substituent, the symmetry of the molecule becomes C _2h , so that the symmetry is increased and the crystallinity is excessively increased. For this reason, the cohesive ability is excessively increased, and the film quality of the polycrystalline film produced by dropping (drop casting) of the solution (ink) and drying thereof is lowered (generally, large crystal grains are precipitated and the uniformity of the film is lowered). The semiconductor characteristics of the film manufactured by such a method are deteriorated. On the other hand, since the compound of the present invention has low symmetry, the aggregating ability is appropriately controlled, and the film quality of the polycrystalline film produced by dropping (drop casting) of the solution (ink) and drying thereof is high. Even a film manufactured by such a method exhibits high semiconductor characteristics.
R ₂₂ is preferably a linear alkyl group having 2 to 12 carbon atoms from the viewpoint of solvent solubility.

  Although the specific example of the compound of this invention is shown below, the compound used by this invention is not limited to these.

(Method for producing dithienobenzodithiophene derivative of the present invention)
The dithienobenzodithiophene derivative of the present invention is the above-mentioned “Production method 1 of the present invention” (provided that R ₂ = R ₂₂ , R ₇ = R ₂₇ , and R ₃ = R ₅ = R ₈ = R ₁₀ = H). "Production method 2 of the present invention" (provided that CH _3- (CH ₂ ) _n = R ₂₂ and R ₁₀₃ = R ₁₀₅ = R ₁₀₈ = R ₁₁₀ = H = R ₂₇ ), Manufacturing method 3 ”(provided that R ₁₀₂ = R ₂₂ , R ₁₀₇ = R ₂₇ , and R ₁₀₃ = R ₁₀₅ = R ₁₀₈ = R ₁₁₀ = H) can be used.
Specific examples are shown below.

  <Manufacturing method 1>

<Manufacturing method 2>

<Manufacturing method 3>

(Organic semiconductor materials and inks)
The compound of the present invention can be used as an organic semiconductor material for organic semiconductor elements. In order to use the compound of the present invention as an organic semiconductor, it is usually used in a film form (an organic semiconductor film or an organic semiconductor layer). The film may be formed by a known dry film forming method such as vacuum deposition, but it can be formed at a low temperature and formed by a wet film forming method (coating method or printing method) excellent in productivity. Therefore, the compound of the present invention, that is, the organic semiconductor material is preferably used as an ink. In order to prepare the ink, the compound of the present invention is dissolved in a solvent. In addition, in order to provide ink characteristics (printability) within a range that does not impair semiconductor characteristics, leveling agents such as fluorine and silicon, and polymers such as polystyrene, acrylic resin, and polymer organic semiconductor compounds, or An oligomer compound can also be added as a viscosity modifier.

Any solvent may be used, or two or more solvents may be mixed and used. Specifically, aliphatic solvents such as n-hexane, n-octane, n-decane and n-dodecane;
Cycloaliphatic solvents such as cyclohexane and methylcyclohexane;
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, tetralin, 1,5-dimethyltetralin, n-propylbenzene, n-butylbenzene, n -Aromatic solvents such as pentylbenzene, 1,3,5-triethylbenzene, 1,3-dimethoxybenzene, 2,5-diethylcybenzene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, benzonitryl;
Tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol diethyl ether (monoglyme), diglyme, triglyme, ethylene glycol monomethyl ether (cellosolve), ethyl cellosolve, propiocellosolve, butyrocellosolve, phenylcellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether Ether solvents such as diethylene glycol propyl ether, diethylene glycol butyl ether, benzyl ethyl ether, ethyl phenyl ether, diphenyl ether, methyl t-butyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether;
Ester solvents such as methyl acetate, ethyl acetate, propylene glycol methyl ether acetate;
Alcohol solvents such as methanol, ethanol, isopropanol; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, 2-hexanone, 2-heptanone, 3-heptanone, acetophenone, propiophenone, butyrophenone;
Other examples include, but are not limited to, dimethylformamide, dimethylsulfoxide, diethylformamide and the like.
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.

  In addition to the compound of the present invention, the organic semiconductor ink of the present invention may have other organic semiconductor materials, that is, an electron donating material, an electron accepting material, an electron transporting material, and a hole transporting material. , A light emitting material, a light absorbing material, and the like may be included. Examples of such materials include π-conjugated polymers or oligomers that exhibit semiconducting properties, non-π conjugated polymers or oligomers 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 film with a high order of molecular arrangement, it is not necessary to perform special printing film formation or special treatment such as thermal annealing, and it is high by simply dropping the ink droplets and drying them. A mobility organic semiconductor film is obtained.

(Organic semiconductor device)
Next, the organic semiconductor element of the present invention will be described. The organic semiconductor element of the present invention is an organic semiconductor element containing the compound of the present invention in an active layer portion (semiconductor layer).

Specific examples of organic semiconductor elements 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; organic EL and light-emitting transistors Light emitting element; temperature sensor, chemical sensor, gas sensor, humidity sensor, radiation sensor, biosensor, blood sensor, immune sensor, artificial retina, taste sensor, pressure sensor, etc .; However, it is not limited to these.
Especially, since the compound of this invention has a high mobility of 1 cm < ² > / Vs or more as an organic semiconductor material, the application to an organic transistor or a light emitting element is especially useful.

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

  Referring to the bottom gate bottom contact type shown in FIG. 1 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.

Here, the bottom gate bottom contact type (hereinafter referred to as BC type) is an organic semiconductor material inferior to other element forming materials (electrode material metal or gate insulating material resin) in terms of heat resistance, weather resistance and solvent resistance. This is a more practical structure since it is treated last in the device manufacturing process. On the other hand, the BC type tends to be inferior to the device characteristics compared to the bottom gate top contact type (hereinafter referred to as the TC type) (Aldrich Material Science Fundamental No. 6 “Basics of Organic Transistors”, section 2.2. ).
The characteristic of the compound of the present invention is that, even if a known compound for organic semiconductor material shows high characteristics in the TC type, the characteristic is not reproduced in the BC type, but as described later, in the BC type, 1 cm ² / Vs or higher mobility. This is because the compound of the present invention forms a polycrystalline film that imparts high mobility with an appropriate cohesive force by simply dropping ink droplets and drying them.

  Glass or resin can be used for the substrate, and a glass sheet, a resin sheet, a plastic film, or the like can be used to obtain a flexible TFT. Among them, it is preferable to use a resin sheet or a plastic film because, in addition to flexibility, the weight can be reduced, the portability can be improved, and the resistance to impact can be improved. Examples of materials include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples thereof include triacetate (TAC) and cellulose acetate propionate (CAP).

  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 It can be used and the like. Furthermore, known and commonly used conductive polymers whose conductivity has been improved by doping, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene and polystyrenesulfonic acid complex (PEDOT / PSS), etc. It can be suitably used.

  As a method for forming an electrode, a method of forming a pattern on an electrode using a known photolithographic method or a lift-off method, using a conductive thin film formed by a method such as vapor deposition or sputtering using the material as a raw material, or the above There is a method of forming a resist pattern on the conductive thin film by thermal transfer or ink jet, and then etching. Alternatively, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by inkjet, or a conductive polymer solution or dispersion, or a conductive fine particle dispersion or paste may be used. Coating may be performed, and the coating film thus obtained may be patterned by lithography or laser ablation. Further, a conductive polymer solution or dispersion, or a conductive fine particle dispersion or paste is applied to a screen printing method, an offset printing method, a gravure offset printing method, a letterpress printing method, a letterpress reverse printing method, a microcontact printing method, or the like. A method of patterning by various printing methods can also be used.

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

  The gate insulating layer is, for example, spin coating method, drop casting method, cast coating method, dip method, die coating method, doctor blade method, wire bar coating method, bar coating method, reverse coating method, air doctor coating method, blade coating method. , Air knife coating method, roll coating method, squeeze coating method, impregnation coating method, transfer roll coating method, kiss coating method, slit coating method, spray coating method, electrostatic coating method, ultrasonic spray coating method, dispensing method, inkjet method, It can be produced by known and commonly used wet film formation methods such as screen printing, gravure printing, offset printing, gravure offset printing, letterpress printing, letterpress reverse printing, and microcontact printing. Depending on the photolithographic method required Patterning may be.

The organic semiconductor layer can be formed by a publicly known dry film forming method such as a vacuum evaporation method using the compound of the present invention, but the ink of the present invention is used for a wet film forming method such as printing. It is preferable to form a film. Although the film thickness of an organic-semiconductor layer is not specifically limited, Usually, it is 0.5 nm-1 micrometer, and it is preferable in it being 2 nm-250 nm.
Further, the organic semiconductor layer may be annealed after film formation, if necessary, for the purpose of improving crystallinity and improving semiconductor characteristics. The annealing temperature is preferably 50 to 200 ° C, more preferably 70 to 200 ° C, and the time is preferably 10 minutes to 12 hours, more preferably 1 hour to 10 hours, and further preferably 30 minutes to 10 hours. .

  Examples of film forming methods include spin coating, drop casting, cast coating, dip, die coating, doctor blade, wire bar coating, bar coating, reverse coating, air doctor coating, and blade coating. Method, air knife coating method, roll coating method, squeeze coating method, impregnation coating method, transfer roll coating method, kiss coating method, slit coating method, spray coating method, electrostatic coating method, ultrasonic spray coating method, dispensing method, inkjet method And known wet film forming methods such as a screen printing method, a gravure printing method, an offset printing method, a gravure offset printing method, a letterpress printing method, a letterpress reverse printing method, and a microcontact printing method.

  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 device. Examples of the display device include a liquid crystal display device, a dispersion type liquid crystal display device, an electrophoretic display device, a particle rotation type display element, an electrochromic display device, an organic EL display device, and electronic paper.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
Example 1 <Production of Compound (1)>

In a 2 L three-necked flask connected with an argon balloon, the compound represented by (1a-b) was changed to H by the method described in Advanced Materials, 2009, Vol. 21, pp. 213-216, and synthesized. Dithienobenzodithiophene (3.02 g, 10 mmol) obtained by performing the above was added to perform argon substitution. Chloroform (1500 mL, manufactured by Kanto Chemical Co., Inc.) was added and dissolved, and then the internal temperature was heated to 60 degrees. A solution prepared by dissolving N-bromosuccinimide (NBS, 1.86 g, 10.5 mmol, manufactured by Kishida Chemical Co., Ltd.) in chloroform (150 mL) was added dropwise. The mixture was stirred for 30 minutes while maintaining 60 degrees, and then cooled to room temperature (the reaction solution turned yellow). Slightly precipitated solid (mainly disubstituted bromine) was removed by filtration, 100 mL of saturated sodium thiosulfate aqueous solution was added to the filtrate, the organic layer was separated by liquid separation operation, dried over anhydrous magnesium sulfate, filtered Then, the solvent was distilled off. The obtained pale yellow solid was dried to obtain 2.8 g (7.3 mmol, 73% yield) of the target α-monobromodithienobenzothiophene.
¹ HNMR (300 MHz, CDCl ₃ ): δ _ppm = 7.33 ₂₅ (d, ³ J _H—H = 5.4 Hz, 1H), 7.33 ₃₀ (s, 1H), 7.54 (d, ³ J _H-H = 5.4 Hz, 1H), 8.22 (s, 1H), 8.29 (s, 1H). Mass (FD ⁺ ): Calcd. forC ₁₄ H ₅ BrS ₄ : m / z = 379.84 and 381.84, Found: 379.89 and 381.88.

To a 500 mL three-necked flask connected with an argon balloon, α-monobromodithienobenzothiophene (2.67 g, 7.0 mmol) obtained by the method described in the above example and tetrakis (triphenylphosphine) palladium (242 mg) were obtained. 0.21 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and copper iodide (40 mg, 0.21 mmol, manufactured by Kanto Chemical Co., Inc.) were added to perform argon substitution. After adding dry toluene (150 mL, manufactured by Kanto Chemical Co., Inc.), the internal temperature was heated to 70 degrees. N, N-diisopropylethylamine (9.8 mL, 70 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) and 1-hexyne (2.4 mL, 21 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise and stirred for 12 hours while maintaining 70 degrees. It was cooled to room temperature (the reaction solution turned black). After adding 100 mL of ion-exchanged water to the reaction solution, the organic layer is separated by a liquid separation operation, dried over anhydrous magnesium sulfate, filtered, and stirred at room temperature for 45 minutes using a metal scavenger to remove transition metals and filtered. Later the solvent was distilled off. The obtained black crude product was purified by silica gel column chromatography (hexane, hexane: chloroform = 98: 2) and dried to obtain the target product α-mono (hex-1-inyl) dithienobenzothiophene. Obtained as a pale yellow solid in 1.04 g (2.7 mmol, 39% yield).
¹ HNMR (300 MHz, CDCl ₃ ): δ _ppm = 0.97 (t, ³ J _H—H = 7.2 Hz, 3 H), 1.4-1.6 (m, 4 H), 2.49 (t, ³ J _H-H = 6.9 Hz, 2 H), 7.31 (s, 1 H), 7.32 (d, ³ J _H-H = 5.1 Hz, 1 H), 7.53 (d, ³ J _{H -H} = 5.1 Hz, 1H), 8.24 (s, 1H), 8.28 (s, 1H). Mass (FD ⁺ ): Calcd. forC ₂₀ H ₁₄ S ₄ : m / z = 382.00, Found: 381.99.

To a 1 L two-necked flask connected with a hydrogen balloon, α-mono (hex-1-ynyl) dithienobenzothiophene (956 mg, 2.5 mmol) obtained by the method described in the above example, and palladium carbon (300 mg, 50% wet) was added to perform hydrogen replacement. After adding THF (100 mL, manufactured by Kanto Chemical Co., Inc.), the mixture was vigorously stirred at room temperature for 48 hours. The reaction solution was filtered through Celite to remove the transition metal, and the solvent was distilled off. The obtained pale yellow crude product was purified by silica gel column chromatography (hexane, hexane: chloroform = 98: 2), and recrystallized by heating using a mixed solvent of acetonitrile: toluene = 90: 10. Α-hexyldithienobenzothiophene was obtained as a colorless solid in 620 mg (1.6 mmol, yield 64%). In addition, by repeating normal phase silica gel column chromatography (hexane / chloroform), reverse phase octadecylsilyl chromatography (acetonitrile / toluene), and recrystallization (acetonitrile / toluene), α having a purity sufficient for evaluation of semiconductor characteristics -120 mg of monohexyl dithienobenzothiophene is obtained.
¹ HNMR (300 MHz, CDCl ₃ ): δ _ppm = 0.90 (t, ³ J _H—H = 7.2 Hz, 3 H), 1.3-1.5 (m. 95 (t, ³ J _H—H) = 7.2 Hz, 2H), 7.01 (s, 1H), 7.32 (d, ³ J _H-H = 5.1 Hz, 1 H), 7.51 (d, ³ J _H-H = 5. 1 Hz, 1 H), 8.20 (s, 1 H), 8.27 (s, 1 H). Mass (FD ⁺ ): Calcd. ForC ₂₀ H ₁₈ S ₄ : m / z = 386.03, Found: 386. 16., 6H), 1.77 (m, 2H)

<Manufacture of organic transistors>
A gate electrode was formed on a glass substrate (corresponding to 1 in FIG. 1) by depositing aluminum with a thickness of about 30 nm by vacuum deposition using a metal mask (corresponding to 2 in FIG. 1). Here, using a parylene vapor deposition apparatus (labor coater PDS2010, manufactured by Japan Parylene), dichloro-diparaxylylene (DPX-C, manufactured by Japan Parylene) as a raw material, a polyparachloroxylylene (Parylene C) thin film (thickness 500 nm) Was formed by a chemical vapor deposition (CVD) method (corresponding to 3 in FIG. 1), and further, a source / drain electrode made of a gold thin film (thickness 40 nm) was patterned by a vacuum deposition method (see FIG. 1). Corresponding to 5 and 6. Channel length L (source electrode-drain electrode interval) was 75 μm and 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 nitrogen blowing to obtain 0.4% p-xylene of the compound (1). An organic semiconductor layer (comprising the compound (1)) is prepared by drop-casting (dropping) 0.1 μL of a solution (organic semiconductor ink) between the source and drain electrodes and then drying by natural concentration. 1 (corresponding to 4 in FIG. 1) was formed (an organic semiconductor layer was formed by dropping (drop casting) droplets of the organic semiconductor solution (ink) and drying it).

<Evaluation of semiconductor characteristics (mobility)>
Semiconductor characteristics (mobility) of the organic transistor thus obtained were evaluated. The semiconductor characteristics (mobility) were measured using a digital multimeter (SMU237, manufactured by Keithley) with a source electrode grounded and -80 V applied to the drain electrode, and a voltage (V _g ) Was swept, the current (I _d ) flowing through the drain electrode was measured, and the value was determined from (Equation 1) from the slope of √I _d −V _g . The unit is cm ² / V · s.

(Wherein, W is the channel width, L is the channel length, μ is the mobility, C is the capacitance per unit area of the gate insulating layer, and V _T is the threshold voltage)
The evaluation results are shown in Table 1.

(Example 2)
<Production of Compound (2)>

Α-Monohexyldithienobenzothiophene (270 mg, 0.7 mmol) obtained by the method described in Example 1 was added to a 300 mL three-necked flask connected with an argon balloon to perform argon substitution. After adding dry THF (30 mL, manufactured by Kanto Chemical Co., Inc.), the mixture was cooled to -78 degrees and stirred for 5 minutes. Normal butyl lithium (0.65 mL, 1.0 mmol, about 1.6 M hexane solution, manufactured by Kanto Chemical Co., Inc.) was added and stirred for 30 minutes while maintaining the internal temperature at -78 degrees (the reaction solution changed to light red). . Iodomethane (0.07 mL, 1.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred while raising the temperature to room temperature over 1 hour (the reaction solution turned pale yellow). After adding 20 mL of saturated aqueous ammonium chloride solution, the organic layer was separated by a liquid separation operation using toluene, dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off. The obtained yellow crude product was purified by silica gel column chromatography (hexane, hexane: toluene = 99: 1), recrystallized by heating using a mixed solvent of acetonitrile: toluene = 90: 10, and dried. The objective product α-hexyl-α'-methyldithienobenzothiophene was obtained as a colorless solid in 150 mg (0.37 mmol, yield 53%). In addition, by repeating normal phase silica gel column chromatography (hexane / toluene), reverse phase octadecylsilyl chromatography (acetonitrile / toluene), and recrystallization (acetonitrile / toluene), α having a purity sufficient for evaluation of semiconductor characteristics 50 mg of hexyl-α'-methyldithienobenzothiophene are obtained.
¹ HNMR (300 MHz, CDCl ₃ ): δ _ppm = 0.90 (t, ³ J _H—H = 6.9 Hz, 3 H), 1.3-1.5 (m, 6 H), 1.76 (m, 2H), 2.64 (d, ⁴ J _H-H = 0.9 Hz, 3 H), 2.94 (t, ³ J _H-H = 7.5 Hz, 2 H), 6.98 (d, ⁴ J _{H −H} = 0.9 Hz, 1H), 6.99 (s, 1H), 8.15 (s, 1H + 1H). Mass (FD ⁺ ): Calcd. forC ₂₁ H ₂₀ S ₄ : m / z = 400.04, Found: 400.04.

<Manufacture of organic transistors and evaluation of semiconductor characteristics (mobility)>
An organic transistor was produced and semiconductor characteristics (mobility) were evaluated in the same manner as in Example 1 except that the compound (2) was used instead of the compound (1). The results are shown in Table 1.

(Example 3)
<Production of Compound (3)>

  2,3-dibromothiophene (2.90 g, 12 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a 1 L three-necked flask connected with an argon balloon to perform argon substitution. After adding dry THF (300 mL, manufactured by Kanto Chemical Co., Inc.), the internal temperature was cooled to -78 degrees. Isopropylmagnesium bromide (12 mL, 12 mmol, 1M tetrahydrofuran solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 minutes, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78 degrees (the reaction solution turned light gray). . To this, zinc bromide anhydride (2.7 g, 12 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 50 mL of dry THF was added dropwise over 5 minutes, followed by stirring while raising the temperature to room temperature over 30 minutes. (The reaction solution is suspended in white) This reaction solution is designated as solution A.

To a 1 L three-necked flask connected with an argon balloon, 1,4-dibromo-2,5-difluorobenzene (2.71 g, 10 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) and tetrakis (triphenylphosphine) palladium (346 mg, 0.30 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to perform argon substitution. After adding dry THF (10 mL, manufactured by Kanto Chemical Co., Inc.), the liquid A prepared by the above method was dropped using a cannula while the internal temperature was fixed at 30 degrees, and the mixture was stirred for 12 hours while maintaining 30 degrees. (The solution turned pale yellow and a white solid was suspended)
The reaction solution was filtered through Celite, 100 mL of 1% aqueous hydrochloric acid solution was added, the organic layer was separated by separation using chloroform, washed with saturated aqueous sodium carbonate solution, dried over anhydrous magnesium sulfate, filtered, and then metal scavenger. The mixture was stirred at room temperature for 45 minutes to remove transition metals, and after filtration, the solvent was distilled off. The obtained brown crude product was purified by silica gel column chromatography (hexane, hexane: THF = 90: 10) and dried to obtain 1-bromo-2,5-difluoro-4- (3- Bromothienyl) benzene was obtained as a colorless solid in 340 mg (0.95 mmol, 8% yield).
¹ HNMR (300 MHz, CDCl ₃ ): δ _ppm = 7.09 (d, ³ J _H-H = 5.4 Hz, 1 H), 7.33 (dd, ³ J _H-F = 7.4 Hz, ⁴ J _{H -F} = 6.6 Hz, 1H), 7.41 (dd, ³ J _H-F = 7.4 Hz, ⁴ J _H-F = 6.6 Hz, 1 H), 7.42 (d, ³ J _H-H = 5.4 Hz, 1 H).

2,3-dibromo-5 prepared by changing R to C ₈ H ₁₇ by a method described in Journal of Materials Chemistry, 2009, Vol. 19, pages 5913-5915, to a 100 mL three-necked flask connected with an argon balloon. -Octylthiophene (713 mg, 2 mmol) was added to perform argon substitution. After adding dry THF (30 mL, manufactured by Kanto Chemical Co., Inc.), the internal temperature was cooled to -78 degrees. Isopropylmagnesium bromide (2 mL, 2 mmol, 1M tetrahydrofuran solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 minute, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78 degrees (the reaction solution turned light gray). . Zinc bromide anhydride (670 mg, 2 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 5 mL of dry THF was added dropwise thereto over 1 minute, and the mixture was stirred while raising the temperature to room temperature over 30 minutes. This reaction solution is designated as solution B (the reaction solution is suspended in white).
To a 300 mL three-necked flask connected with an argon balloon, 1-bromo-2,5-difluoro-4- (3-bromothienyl) benzene (353 mg, 1 mmol) obtained by the method described in the above example, and tetrakis ( Triphenylphosphine) palladium (34 mg, 0.03 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to perform argon substitution. After adding dry THF (3 mL, manufactured by Kanto Chemical Co., Inc.), the liquid B prepared by the above method was added dropwise using a cannula, heated to 65 degrees and stirred for 12 hours. (The solution turned pale yellow and a white solid was suspended)

The reaction solution was filtered through Celite, 30 mL of 1% aqueous hydrochloric acid solution was added, the organic layer was separated by separation using chloroform, washed with saturated aqueous sodium carbonate solution, dried over anhydrous magnesium sulfate, filtered, and then metal scavenger. The mixture was stirred at room temperature for 45 minutes to remove transition metals, and after filtration, the solvent was distilled off. The obtained brown crude product was purified by silica gel column chromatography (hexane, hexane: THF = 90: 10), and further purified by reverse phase octadecyl silica column chromatography (methanol, methanol: THF = 50: 50), When dried, 210 mg (0.38 mmol, 38% yield) of 1,4-difluoro-2- (3-bromothienyl) -5- (3-bromo-5-octylthienyl) benzene, which is the target product, is colorless. Obtained as a solid. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm = 0.89 (t, ³ J _H—H = 6.9 Hz, 3 H), 1.2-1.4 (m, 10 H), 1.69 (m , 2H), 2.80 (t, ³ J _H-H = 7.5 Hz, 2 H), 6.79 (s, 1 H), 7.10 (d, ³ J _H-H = 5.4 Hz, 1H), 7.36 (m, 1H), 7.39 (m, 1H), 7.42 (d, ³ J _H−H = 5.4 Hz, 1H).

1,4-Difluoro-2- (3-bromothienyl) -5- (3-bromo-5-octylthienyl) benzene obtained by the method described in the above Example was added to a 100 mL two-necked flask connected with an argon balloon. (210 mg, 0.38 mmol) and sodium sulfide nonahydrate (288 mg, 1.2 mmol, manufactured by Kanto Chemical Co., Inc.) were added to perform argon substitution. After adding N-methylpyrrolidone (10 mL, manufactured by Kanto Chemical Co., Inc.), the internal temperature was heated to 180 ° C. and stirred for 3 hours (the reaction solution turned brown). 90 mL of a saturated aqueous solution of ammonium chloride was added thereto to precipitate a solid, and the solid obtained after suction filtration was washed with methanol. The resulting pale yellow crude product is purified by silica gel column chromatography (hexane, hexane: toluene = 99: 1), recrystallized by heating using a mixed solvent of acetonitrile: toluene = 90: 10, and dried. Thus, α-monooctyldithienobenzothiophene, which was the target product, was obtained as a colorless solid in 100 mg (0.24 mmol, yield 60%). In addition, 20 mg of α-monooctyldithienobenzothiophene having sufficient purity for evaluation of semiconductor characteristics was obtained by repeating recrystallization. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm = 0.88 (t, ³ J _H—H = 6.9 Hz, 3 H), 1.2-1.4 (m, 10 H), 1.77 (m , 2H), 2.91 (t, ³ J _H−H = 7.2 Hz, 2H), 7.01 (s, 1H), 7.31 (d, ³ J _H−H = 5.1 Hz, 1H), 7.51 (d, ³ J _H−H = 5.1 Hz, 1H), 8.20 (s, 1H), 8.27 (s, 1H). Mass (FD ⁺ ): Calcd. for C ₂₂ H ₂₂ S ₄ : m / z = 414.06, Found: 414.06.

<Manufacture of organic transistors and evaluation of semiconductor characteristics (mobility)>
An organic transistor was produced and semiconductor characteristics (mobility) were evaluated in the same manner as in Example 1 except that the compound (3) was used instead of the compound (1). The results are shown in Table 1.

(Comparative Example 1)
The compound represented by (1 ′) was produced by the method described in WO2006 / 077788. Thereafter, production of an organic transistor and evaluation of semiconductor characteristics (mobility) were carried out in the same manner as in Example 1 except that the compound (1 ′) was used instead of the compound (1). The results are shown in Table 1.

(Comparative Example 2)
A compound represented by (2 ′) was produced by the method described in Advanced Materials, 2009, Vol. 21, pp. 213-216. Thereafter, production of an organic transistor and evaluation of semiconductor characteristics (mobility) were carried out in the same manner as in Example 1 except that the compound (2 ′) was used instead of the compound (1). The results are shown in Table 1.

  As is clear from Table 1, the compound of the present invention is excellent in solvent solubility and is a simple wet film-forming method without passing through a complicated process (that is, a solution (ink) droplet is dropped and dried itself). Thus, a BC transistor having high semiconductor characteristics (mobility) can be formed. On the other hand, the known and conventional compounds shown in Comparative Examples 1 and 2 cannot exhibit high mobility by such a simple film formation method. 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. Therefore, it is clear that the production method of the present invention, which can give the compound of the present invention, is superior to known and conventional production methods.

  The compound of the present invention can be used as an organic semiconductor material, and can be used for an organic transistor using the compound of the present invention 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 (11)

A method for producing a dithienobenzodithiophene derivative represented by the general formula (A), which comprises the following steps (I) to (IV):
(I) a first step of converting a compound represented by the general formula (B) into an organometallic compound (B) ′ having X ₅ as an active site;
(II) a second step of producing a compound represented by the general formula (D) by cross-coupling the organometallic compound (B) ′ with the compound represented by the general formula (C);
(III) a third step of converting the compound represented by the general formula (E) into an organometallic compound (E) ′ having X ₇ as an active site;
(IV) A fourth step of producing a compound represented by the general formula (F) by cross-coupling the organometallic compound (E) ′ with the compound represented by the general formula (D).

(In each formula, X _{1 to} X ₈ represent a halogen atom, and R ₂ , R ₃ , R ₅ , R ₇ , R ₈ and R ₁₀ represent a hydrogen atom or an arbitrary substituent.) R ₂ , R ₃ , R ₅ , R ₇ , R ₈ and R ₁₀ are each independently a hydrogen atom, an acyclic or cyclic alkyl group having 1 to 20 carbon atoms (- In order that CH ₂ — is not directly bonded to an oxygen atom, a sulfur atom, or a nitrogen atom, —O—, —R′C═CR′—, —CO—, —OCO—, —COO—, —S—, _{-SO 2 -, - SO -,} - NH -, - NR'- or -C≡C- may be substituted with a hydrogen atom in the alkyl group, a substituted aromatic group, the halogeno group, or a nitrile group (Wherein R ′ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms)), a halogeno group, an aromatic group (the aromatic group may be acyclic or cyclic). Substituted with an alkyl group of 1 to 20 carbon atoms, a halogeno group, an aromatic group, or a nitrile group of the formula Ku, -CH ₂ in the alkyl group - is an oxygen atom, such sulfur atoms and nitrogen atoms are not bonded each directly, -O -, - CR '' = CR '' -, - CO -, - OCO- , —COO—, —S—, —SO ₂ —, —SO—, —NH—, —NR ″ — or —C≡C—, and the hydrogen atom in the alkyl group is aromatic Group, halogeno group, or nitrile group (where R ″ represents an acyclic or cyclic alkyl group having 1 to 20 carbon atoms)), a nitro group, or a nitrile group The manufacturing method of Claim 1 which exists. For R ₂ , R ₃ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₂ and R ₇ are the same or different, R ₃ and R ₈ are the same or different, and R ₅ and R ₁₀ are the same, The production method according to claim 1 or 2, wherein at least one of the two combinations of R ₂ and R ₇ and R ₃ and R ₈ is different from each other. A method for producing a dithienobenzodithiophene derivative represented by the general formula (G), which comprises the following steps (I) to (III).
(I) a first step of producing a compound represented by the general formula (I) by monohalogenating a compound represented by the general formula (H) in the presence of N-halosuccinimide;
(II) A compound represented by general formula (I) and a compound represented by general formula (J) or general formula (K) are subjected to a cross-coupling reaction in the presence of a transition metal catalyst, A second step for producing the compound represented,
(III) The compound represented by the general formula (L) is subjected to catalytic hydrogen reduction in the presence of a heterogeneous transition metal catalyst or a homogeneous transition metal catalyst to obtain a dithienobenzodithiophene derivative represented by the general formula (G). Third process to manufacture.

(In each formula, R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ represent a hydrogen atom or an arbitrary substituent, X ₁₁ represents a halogen atom, and Y ₁₁ − represents CH ₃ — (CH ₂ ) _n−2 −. C≡C— or CH ₃ — (CH ₂ ) _n−2 —CH═CH—, where n represents an integer of 2 to 19. A method for producing a dithienobenzodithiophene derivative represented by the general formula (M), wherein the dithienobenzodithiophene derivative represented by the general formula (G) ′ is represented by the general formula (m) in the presence of organolithium. A method for producing a dithienobenzodithiophene derivative represented by the general formula (M), comprising a step of reacting an alkyl halide to produce a dithienobenzodithiophene derivative represented by the general formula (M).

(In each formula, R ₁₀₂ represents an alkyl group having 1 to 20 carbon atoms, R ₁₀₇ represents an alkyl group having 1 to 20 carbon atoms, and R ₁₀₃ , R ₁₀₅ , R ₁₀₈ and R ₁₁₀ are hydrogen atoms or Represents an arbitrary substituent, and X ₁₂ represents a halogen atom, provided that R ₁₀₂ and R ₁₀₇ are different. A dithienobenzodithiophene derivative represented by the general formula (N).

(In the formula, R ₂₂ represents a linear alkyl group having 2 to 20 carbon atoms, and R ₂₇ represents a hydrogen atom or a methyl group.) An organic semiconductor material containing the dithienobenzodithiophene derivative according to claim 6. An organic semiconductor ink containing the organic semiconductor material according to claim 7. An organic semiconductor film containing the organic semiconductor material according to claim 7. The organic-semiconductor element containing the organic-semiconductor material of Claim 7. An organic transistor containing the organic semiconductor material according to claim 7.

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