JP2015078174A - Compound production method and compound obtained by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an efficient production method of a compound excellent in a semiconductor property, and a production method of an intermediate of the compound.SOLUTION: Provided is a production method of a halogenated compound, by making a halogenation agent such as bromine react with [1] benzothieno[3,2-b][1]benzothiophene, for obtaining a halogenated compound expressed by formula (B-1). Also provided is a production method of a derivative expressed by formula (C-1) obtained by making the halogenated compound react with a boron compound under the presence of a palladium catalyst.

Description

  The present invention relates to a method for producing an organic semiconductor material effective for an organic thin film transistor.

  Conventionally, a thin film transistor (TFT) using amorphous silicon or polycrystalline silicon has been widely used as a switching element for liquid crystal display devices, organic EL display devices and the like. However, these TFTs using silicon cannot be developed on a plastic substrate having poor heat resistance because the manufacturing equipment is expensive and the film is formed at a high temperature. In order to solve this problem, an organic TFT using an organic semiconductor as a channel semiconductor layer instead of a silicon semiconductor has been proposed.

  Since an organic semiconductor can be formed into a solution at a low temperature to form a printed film, it does not require a large-scale manufacturing facility and can be applied to plastics with poor heat resistance, and is expected to lead flexible displays. On the other hand, organic semiconductors have lower carrier mobility than silicon semiconductors, and as a result, the response speed of TFTs has been a problem for practical use. Recently, organic semiconductors with the same mobility as amorphous silicon have been developed. It has been.

For example, Patent Document 1 discloses 2,7-substituted [1] benzothieno [3,2-b] [1] benzothiophene skeleton (hereinafter referred to as [1] benzothieno [3,2-b] [1] benzothiophene. compounds having abbreviated as BTBT) are described, as a substituent, _halogen, C 1 _{-C 18} alkyl, _C 1 _{-C 18} alkyl having _halogen, C 1 _{-C 18 alkyloxy,} C 1 -C ₁₈ alkylthio, or aryl, or is aryl having _halogen, C 1 _{-C 18} alkyl, _C 1 _{-C 18} alkyl having _halogen, C 1 _{-C 18 alkyloxy,} at least one C 1 _{-C 18} alkylthio Things are listed. That the mobility of these compounds ^(cm 2 / Vs) is 0.17~0.31cm ² / Vs.

Patent Document 2 describes a compound having a 2,7-substituted BTBT skeleton, and the substituent is a hydrogen atom or a halogeno-substituted C ₁ -C ₃₆ aliphatic hydrocarbon group. ing. The mobility of these compounds ^(cm 2 / Vs) has been described to be 0.12~4.5cm ² / Vs. In these compounds, the same substituent is modified at the symmetrical position of BTBT and can be easily manufactured by a known method. However, in order to obtain a film with high mobility, the annealing temperature during film formation is set to be low. There are still problems in practical use such as control.

On the other hand, Patent Document 3 discloses 2-alkyl-7-aryl BTBT. This compound can easily form a film having a high molecular order by crystallizing via a higher-order liquid crystal phase, and a film having a high mobility reaching 5 cm ² / Vs. It can be given easily. However, since this compound has to introduce two different substituents into BTBT, the synthesis route becomes complicated, and the conventional production method cannot obtain the target product in high yield. It was.

WO2006-077788 WO2008-47896 WO2012-121393

  The subject of this invention is providing the manufacturing method of the compound which is excellent in a semiconductor characteristic, and the manufacturing method of the precursor of this compound.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by providing the following production method.

  A method for producing a halogenated compound B, comprising reacting a compound A represented by the following formula (1) with a halogenating agent to obtain a halogenated compound B represented by the following formula (2).

・・・（１）

... (1)

・・・（２）

... (2)

(In the above formulas (1) and (2), X represents any of a sulfur atom, an oxygen atom and a selenium atom, R ₁ represents an alkylene group having 1 to 20 carbon atoms, or an alicyclic group, R ₂ represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group, or a hydrogen atom, R ₃ represents a halogen atom, and Ar represents an aromatic hydrocarbon group or heteroaromatic which may have a substituent. Y represents S, O, or NH, and m and n each independently represent 0 or 1. However, when n is 0, R ₁ terminal is a hydrogen atom or a halogen atom. .)

  Moreover, the halogenated compound B obtained by the said manufacturing method is derivatized, The compound C represented by Formula (3) is obtained, The manufacturing method of the compound C characterized by the above-mentioned is provided.

・・・（３）

... (3)

(In the above formula (3), X, Y, m, n, Ar, R ₁ and R ₂ are the same as those in the above formulas (1) and (2), and R ₄ has a substituent. It may be an aromatic hydrocarbon group or a heteroaromatic group, an alkenyl group, an alkynyl group, a group represented by the following general formula (4) or (5).

(Ar ₁ is an aromatic hydrocarbon group or heteroaromatic group which may have a substituent, Ar ₂ is an aromatic hydrocarbon group which may have a substituent, R ′ is a hydrogen atom, A trialkylsilyl group having an alkyl group of 4, an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, * represents a bonding site.)

  Moreover, the organic-semiconductor material containing the compound C obtained by the said manufacturing method is provided.

  By using the production method of the present invention, the number of production steps can be shortened, and an asymmetric BTBT having different substituents can be produced simply and efficiently.

Hereinafter, the present invention will be described in detail.
The first invention of the present invention provides a process for producing a halogenated compound B represented by the general formula (2) by reacting the compound A represented by the general formula (1) with a halogenating agent. It is.

(In the above formulas (1) and (2),
X represents a sulfur atom, an oxygen atom, or a selenium atom,
Ar is an optionally substituted aromatic hydrocarbon or heteroaromatic ring,
R ₁ represents either an alkylene group having 1 to 20 carbon atoms or an alicyclic group,
Y represents O, S, or NH;
R ₂ represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group, or a hydrogen atom,
R ₃ represents a halogen atom,
n and m each independently represents 0 or 1. However, when n is 0, the R ₁ terminal is a hydrogen atom or a halogen atom. )

(Description of Compound A)
First, the compound A of the general formula (1) that can be used in the present invention will be described.
X represents any of a sulfur atom, an oxygen atom, and a selenium atom, and X is preferably a sulfur atom because of its high mobility and stability in the atmosphere.
Specific examples of the substituent represented by *-(Ar) _m -R _1- (YR ₂ ) _n include (I) an alkyl group having 1 to 20 carbon atoms, and (II) 5 to 20 carbon atoms. (III) an alkyl group having 1 to 20 carbon atoms having a halogen atom at the terminal, (IV) an alkoxyalkyl group having 2 to 20 carbon atoms, and (V) an alkylsulfanylalkyl group having 2 to 20 carbon atoms. (VI) an alkylaminoalkyl group having 2 to 20 carbon atoms, (VII) an aromatic hydrocarbon group optionally having an alkyl group having 1 to 20 carbon atoms, and (VIII) an alkyl group having 1 to 20 carbon atoms. It is a heteroaromatic group which may have, and each can be illustrated as follows.

(I) 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, 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, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradec Le group, n- pentadecyl, n- hexadecyl group, n- heptadecyl group, n- octadecyl group, and a linear or branched alkyl group, such as n- eicosyl group,
Furthermore, a 2,2,3,3,3-pentafluoropropyl group in which a part of hydrogen atoms of these alkyl groups having 1 to 20 carbon atoms is substituted with a fluorine atom, 2,2,3,3,4, 4,4-heptafluorobutyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5,6, Halogen-substituted alkyl such as 6,6-undecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl group Groups can also be used.

(II) Examples of the alicyclic group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 4-methylcyclohexyl group, a dicyclopentanyl group, a tricyclodecanyl group, and a cyclohexylmethyl group.

(III) As a C1-C20 alkyl group which has a halogen atom at the terminal, for example, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-iodoethyl group, 3-chloro Propyl group, 3-bromopropyl group, 3-iodopropyl group, 4-chlorobutyl group, 4-bromobutyl group, 4-iodobutyl group, 5-chloropentyl group, 5-bromopentyl group, 5-iodopentyl group, 6- Chlorohexyl group, 6-bromohexyl group, 6-iodohexyl group, 7-chloroheptyl group, 7-bromoheptyl group, 7-iodoheptyl group, 8-chlorooctyl group, 8-bromooctyl group, 8-iodooctyl Group, 9-chlorononyl group, 9-bromononyl group, 9-iodononyl group, 10-chlorodecyl group, 10- Lodecyl group, 10-iododecyl group, 11-chloroundecyl group, 11-bromoundecyl group, 11-iodoundecyl group, 12-chlorododecyl group, 12-bromododecyl group, 12-iodododecyl group, 13-chloro Tridecyl group, 13-bromotridecyl group, 13-iodotridecyl group, 14-chlorotetradecyl group, 14-bromotetradecyl group, 14-iodotetradecyl group, 15-bromopentadecyl group 16-bromohexyldecyl Group, 17-bromoheptadecyl group, 18-bromooctadecyl group, 20-bromoeicosyl group and the like.

(IV) As an alkoxyalkyl group having 2 to 20 carbon atoms, 2-ethoxyethyl group, 2-butoxyethyl group, 2-n-hexyloxyethyl group, 2-n-heptyloxyethyl group, 2-n-tetra Examples include decyloxyethyl group, 2-cyclohexyloxyethyl group, 12-ethoxydodecyl group, cyclohexyloxyethyl group and the like.

(V) Examples of the alkylsulfanylalkyl group having 2 to 20 carbon atoms include a methylsulfanylpropyl group, a 2-n-hexylsulfanylethyl group, a 3-n-decylsulfanylpropyl group, a cyclohexylsulfanylpropyl group, and an 8-methylsulfanyloctyl group. , 8-ethylsulfanyloctyl group, 8-propylsulfanyloctyl group, 10-ethylsulfanyldecyl group, and the like.

(VI) As a C2-C20 alkylaminoalkyl group, a methylaminopropyl group, 2-n-hexylaminoethyl group, 3-n-decylaminopropyl group, cyclohexylaminopropyl group, 8-methylaminooctyl group , 8-ethylaminooctyl group, 8-propylaminooctyl group, 10-ethylaminodecyl group and the like.

(VII) Examples of the aromatic hydrocarbon group which may have an alkyl group having 1 to 20 carbon atoms include, for example, a phenyl group, a naphthyl group and an azulenyl group having an alkyl group having 1 to 20 carbon atoms described in (I) above. A monocyclic or polycyclic group having 6 to 24 carbon atoms, such as a group, acenaphthenyl group, anthranyl group, phenanthryl group, naphthacenyl group, fluorenyl group, pyrenyl group, chrysenyl group, perylenyl group, biphenyl group, p-terphenyl group, and quarterphenyl group Examples thereof include a cyclic aromatic hydrocarbon group.

(VIII) Examples of the heteroaromatic group which may have an alkyl group having 1 to 20 carbon atoms include, for example, a pyrrolyl group, an indolyl group, and a furyl group having an alkyl group having 1 to 20 carbon atoms described in (I) above. , Thienyl group, thienothienyl group, thienoimidazolyl group, benzofuryl group, triazolyl group, benzotriazolyl group, benzothienyl group, pyrazolyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl Group, indolinyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, thiadiazinyl group, oxadiazolyl group, benzoquinolinyl group, thiadiazolyl group, pyrrolothiazolyl group, pyrrolopyridazinyl group, tetrazolyl group, oxazolyl group, etc. 5-member ring Heteroaromatic groups and the 6-membered ring, and the like polycyclic heteroaromatic group which benzene is fused to said plurality containing aromatic groups.
Among the above substituents, (I) an alkyl group having 1 to 20 carbon atoms or (III) an alkyl group having 1 to 20 carbon atoms having a halogen atom at the terminal has few side reactions and a high reaction yield. To preferred.

  Further, Compound A represented by the general formula (1) was obtained by subjecting BTBT to acyl chloride and Friedel-Crafts acylation reaction by a known and conventional method described in, for example, Liquid Crystals 31, 137-1380 (2004). Thereafter, it can be obtained by reducing the carbonyl group. As the reaction solvent for Friedel-Crafts acylation reaction, for example, halogen solvents such as dichloromethane, chloroform, 1,1,2-trichloroethane can be used, and as the catalyst, aluminum chloride, aluminum bromide, zinc chloride, Metal halides such as iron chloride can be used. For reduction of the acyl group, a known and commonly used reduction method such as Wolf-Kishner reduction using hydrazine or catalytic reduction with hydrogen can be applied. Although reaction temperature does not have a restriction | limiting in particular, It is preferable from the point of reaction rate to react in the range of -70 to 100 degreeC.

(Synthesis of Halogenated Compound B)
The halogenated compound B represented by the general formula (2) can be obtained by reacting the above compound A with a halogenating agent. As the halogenating agent, known ones may be used. Examples of the iodinating agent include iodine, benzyltrimethylammonium dichloroiodate, bis (pyridine) iodonium tetrafluoroborate, 1-chloro-2-iodoethane, Examples include 1,3-diiodo-5,5-dimethylhydantoin, N-iodosaccharin, N-iodosuccinimide, iodine monochloride, iodine trichloride.

  Examples of brominating agents include benzyltrimethylammonium tribromide, bromine, N-bromoacetamide, 2-bromo-2--2-cyano-N, N-dimethylacetamide, N-bromophthalimide, N-bromosaccharin, N- Examples include bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, di- or tribromoisocyanuric acid, tetrabutylammonium tribromide, and the like.

  Examples of the chlorinating agent include benzyltrimethylammonium tetrachloroiodide salt, tert-butyl hypochlorite, N-chlorophthalimide, N-chlorosuccinimide, di- or trichloroisocyanuric acid, and the like.

  The addition amount of the halogenating agent is preferably 0.5 to 3 equivalents relative to Compound A. If it is 0.5 equivalent or more, the reaction amount of the halogenation reaction is large, and if it is 3 equivalent or less, the halogen easily reacts selectively with the aromatic ring, which is preferable. More preferably, it is 0.8-2.0 equivalent.

The reaction solvent may be any solvent that does not react with the halogenating agent. Acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,4-dioxane, tetrahydrofuran, dimethoxyethane, chloroform, dichloromethane, acetic acid, sulfuric acid, Furthermore, the solvent etc. which mixed 2 or more types of these solvents can be used. Among the above solvents, chloroform, dichloromethane, acetic acid, or a mixed solvent thereof is preferable because of its high selectivity to the target substitution position and fast reaction. The reaction can be performed at a temperature of -78 ° C to 150 ° C. From the reaction rate, −30 ° C. or higher is preferable, and 50 ° C. or lower is preferable for suppressing the formation of by-products such as isomers.
Furthermore, in order to increase the yield of the halogenated compound B, there is no problem even if a catalyst is used in combination. The catalyst is not limited as long as it increases the yield of the halogenated compound B, and examples thereof include metals such as iron and aluminum, metal halides thereof, acids such as acetic acid and sulfuric acid, and iodine.

Further, potassium iodide or the like can be added to the brominated compound B to replace it with an iodide.

In addition, in the halogenation reaction, in addition to the halogenated compound B represented by the following formula (2), the following formulas (6), (7) and (8) which are isomers are formed. Although it may be used in the next step as it is, in order to increase the yield and purity of the next step, a halogenated compound B is used by using a known and conventional purification method such as recrystallization, silica gel column chromatography, or sublimation purification. Can be easily isolated.

・・・（２）

... (2)

・・・（６）

... (6)

・・・（７）

... (7)

・・・（８）

... (8)

Among these purification methods, purification by recrystallization is preferable from the viewpoint of equipment and productivity.
The organic solvent used for recrystallization is not particularly limited, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, ligroin, hexane, heptane, cyclohexane, etc. Hydrocarbon solvents, diethyl ether, diisopropyl ether, ether solvents such as methylglyme, aromatic solvents such as toluene, o-xylene, m-xylene, p-xylene, halogen solvents such as dichloromethane, chloroform, etc. A publicly known organic solvent can be used. These organic solvents can be used alone or in a mixture.

The organic solvent used for recrystallization can be variously selected depending on the properties of the compound to be obtained. However, the compounds of the general formulas (6), (7) and (8) have high solubility, and the halogenated compound (B) A ketone solvent such as acetone and a hydrocarbon solvent such as cyclohexane are preferable because they are obtained in high yield.
On the other hand, the compounds of the general formulas (6), (7), and (8) can be isolated by silica gel chromatography or sublimation purification, and each may be used as a precursor of an organic semiconductor material.

[Synthesis of Compound C]
Next, the manufacturing method of the compound C which is 2nd invention is demonstrated.

(In General Formulas (2) and (3), X, Y, Ar, m, n, R ₁ , R ₂ , and R ₃ are the same as described above, and R ₄ may have a substituent. A good aromatic hydrocarbon group or heteroaromatic group, alkenyl group, alkynyl group, group represented by the following general formula (4) or (5).

(Ar ₁ is an aromatic hydrocarbon group or heteroaromatic group which may have a substituent, Ar ₂ is an aromatic hydrocarbon group which may have a substituent, R ′ is a hydrogen atom, A trialkylsilyl group having 4 alkyl groups, an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent.))

  Compound B having a halogen atom as a substituent obtained in the first step of the present invention is subjected to known and commonly used coupling reactions with various boron compounds, allyl compounds, ethynyl aryl compounds, or halogenated aryl compounds. Compound C useful as an organic semiconductor material can be obtained. As the coupling reaction, known and conventional methods such as Suzuki-Miyaura coupling, Sonogashira coupling, Mizoroki-Heck reaction, Kumada-Tamao coupling, etc. can be applied. For these reaction conditions and catalysts, for example, Chemical Reviews such as Review 95, 2457-2483 (1995) and Chemical Review 111, 1417-1492 (2011), and cross-coupling reactions-fundamentals and industrial applications-(CMC Publishing) The methods and conditions described in the above can be applied.

  The reaction is not particularly limited, and a known and commonly used reagent can be used, and any reaction temperature and any well-known and commonly used temperature can be applied.

  Examples of boron compounds that can be used include phenylboronic acid, 4-hydroxyphenylboronic acid, 2-methylphenylboronic acid, 4-tert-butylphenylboronic acid, 3-methoxyphenylboronic acid, 4-phenoxyphenylboronic acid, 2- Chloro-4-methylphenylboronic acid, 4- (phenylethynyl) phenylboronic acid and their boric acid pinacol esters, in addition to phenylboric acid derivatives, naphthalene boric acid derivatives, anthracene boric acid derivatives, thiophene boric acid derivatives, benzothiophene Various aromatic boric acid derivatives such as boric acid derivatives can be mentioned.

  Examples of ethynylaryl compounds include ethynylbenzene, 2-ethynylnaphthalene, 1-ethynylnaphthalene, 4-ethynyltoluene, 1-ethynyl-4-ethylbenzene, 1-ethynyl-4-n-propylbenzene, 1-ethynyl-4-isopropyl. Benzene, 1-ethynyl-4-n-butylbenzene, 1-ethynyl-4-t-butylbenzene, 1-ethynyl-4-amylbenzene, 1-ethynyl-4-n-hexylbenzene, 2-ethynyl-1, 4-dimethylbenzene, 9-ethynylphenanthrene, ethynylaniline, (4-ethynylphenyl) methanol, 3-ethynylphenol, 1-ethynyl-4-pentylbenzene, 1-bromo-4-ethynylbenzene, 1-bromo-3- Ethynylbenzene, 4-ethynyl-1-fluoro-2-me Tylbenzene, 1-ethynyl-2,4-difluorobenzene, 5-ethynyl-1,2,3-trifluorobenzene, benzyl-4-ethynylphenyl ether, 1-ethynyl-4- (trifluoromethoxy) benzene, 2- Ethynylthiophene, 2-ethynyl-3-methylthiophene, 5-ethynyl-2, 3-dimethylthiophene, 2-ethynyl-5-ethynylthiophene, 2-chloro-5-ethynylthiophene, 2-bromo-5-ethynylthiophene, Examples include 2-ethynylpyridine, 3-ethynylpyridine, 4-ethynylpyridine, and the like.

  Examples of the palladium catalyst that can be used when reacting the halogenated compound B with the boron compound include bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon, and the like. Compound C can be produced by reacting in the presence of a base.

When the halogenated compound B is reacted with the ethynyl aryl compound, examples of the palladium catalyst that can be used include bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, and palladium / carbon. Compound C can be produced by reacting in the presence of copper iodide and a base.

  By using the production method of the present invention, the compound C having an asymmetric structure, which is excellent as an organic semiconductor material, can be produced efficiently.

(Compound C)
The substituent R ₄ of the compound C represented by the general formula (3) obtained as described above is an aromatic hydrocarbon group or heteroaromatic group which may have a substituent, an alkenyl group, an alkynyl group, It is group represented by the following general formula (4) or (5).

(Ar ₁ is an aromatic hydrocarbon group or heteroaromatic group which may have a substituent, Ar ₂ is an aromatic hydrocarbon group which may have a substituent, R ′ is a hydrogen atom, A trialkylsilyl group having an alkyl group of 4, an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, * represents a bonding site.)

The aromatic hydrocarbon group or heteroaromatic group which may have the above substituent is an aromatic hydrocarbon group having 6 to 24 carbon atoms composed of carbon and hydrogen, or an oxygen atom, a nitrogen atom, It is a C5-C24 heteroaromatic group containing a sulfur atom, etc., and these may have a C1-C6 alkyl group and a halogen atom as a substituent. Examples of the aromatic hydrocarbon group that may have such a substituent include a phenyl group, a naphthyl group, an azulenyl group, an acenaphthenyl group, an anthranyl group, a phenanthryl group, a naphthacenyl group, a fluorenyl group, a pyrenyl group, and a chrysenyl group. Perylenyl group, biphenyl group, p-terphenyl group, quarterphenyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, mesityl group, duryl Group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n- Aromatic hydrocarbon having alkyl group such as decaphenyl group, 4-stearylphenyl group, 9,9′-dihexylfluorenyl group A primary group; a 4-fluorophenylene group, a 2,6-fluorophenylene group, a 4-chlorophenylene group, a 2,3,4,5,6-perfluorophenylene group, or the like, and the arylene group is a fluorine atom, a chlorine atom, Aromatic hydrocarbon groups substituted with halogen such as bromine atom, and heteroaromatic groups which may have a substituent include pyridinyl group, pyrrole group, thienyl group, benzothienyl group, benzoxazolyl group Benzothiazolyl group, oxadiazolyl group, dibenzooxazolyl group, dibenzothienyl group; heteroaromatic group having an alkyl group such as 2-methylthienyl group, 2-butylthienyl group, 2-hexylthienyl group;
Methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, 4- (2-ethoxyethyl) phenyl group, 4- (2-n-hexyloxyethyl) phenyl group, 4- (2-n-heptyloxyethyl) phenyl group 4- (2-n-tetradecyloxyethyl) phenyl group, 4- (2-cyclohexyloxyethyl) phenyl group, 4- (12-ethoxydodecyl) phenyl group, 4- (cyclohexyloxyethyl) phenyl group, ethoxy Naphthyl group, 5- (2-ethoxyethyl) thienyl group, 5- (2-n-tetradecyloxyethyl) thienyl group, 5- (2-cyclohexyloxyethyl) thienyl group, 5- (12-ethoxydodecyl) thienyl group An alkoxyaryl group or an alkoxyalkylaryl group such as a group;
4- (methylsulfanylpropyl) phenyl group, 4- (2-n-hexylsulfanylethyl) phenyl group, 4- (3-n-decylsulfanylpropyl) phenyl group, 4- (cyclohexylsulfanylpropyl) phenyl group, 5- Alkylsulfanyl aryl such as (methylsulfanylpropyl) thienyl group, 5- (2-n-hexylsulfanylethyl) thienyl group, 5- (3-n-decylsulfanylpropyl) thienyl group, 5- (cyclohexylsulfanylpropyl) thienyl group A group or an alkylsulfanylalkylaryl group;
Ethylaminophenyl group, 4- (3-octylaminopropyl) phenyl group, 4- (3-dodecylaminopropyl) phenyl group, 4- (diethylaminoethyl) phenyl group, 5- (3-octylaminopropyl) thienyl group, Examples include alkylamino or alkylaminoalkylaryl groups such as 5- (3-dodecylaminopropyl) thienyl group and 5- (diethylaminoethyl) thienyl group.
Examples of the alkenyl group include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, methylpentenyl group, cyclohexene, 4 -Linear, branched and cyclic alkenyl groups such as methylcyclohexene.

Examples of the alkynyl group include ethenyl group, 1-propenyl group, 2-propenyl (propargyl) group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group, 1-octenyl group, Nonenyl group, 1-decenyl group, 1-undecenyl group, 1-dodecenyl group, 1-tridecenyl group, 1-tetradecenyl group, 1-pentadecenyl group, 1-hexadecenyl group, 1-heptadecenyl group, 1-octadecenyl group, 1-octadecenyl group A nonadecenyl group, and the like.

The substituent represented by the general formula (4) is an arylethynyl group, for example, a phenylethynyl group, a naphthylethynyl group, a thienylethynyl group, an oxazolylethynyl group;
Methoxyphenylethynyl group, ethoxyphenylethynyl group, butoxyphenylethynyl group, 4- (2-ethoxyethyl) phenylethynyl group, 4- (2-n-hexyloxyethyl) phenylethynyl group, 4- (2-n-heptyl) Oxyethyl) phenylethynyl group, 4- (2-n-tetradecyloxyethyl) phenylethynyl group, 4- (2-cyclohexyloxyethyl) phenylethynyl group, 4- (12-ethoxydodecyl) phenylethynyl group, 4- (Cyclohexyloxyethyl) phenylethynyl group, 5- (2-ethoxyethyl) thienylethynyl group, 5- (2-n-tetradecyloxyethyl) thienylethynyl group, 5- (2-cyclohexyloxyethyl) thienylethynyl group, 5- (12-Ethoxydodecyl) thienyl Alkoxy or alkoxyalkyl arylene ethynyl group such as ethynyl group;
4- (methylsulfanylpropyl) phenylethynyl group, 4- (2-n-hexylsulfanylethyl) phenylethynyl group, 4- (3-n-decylsulfanylpropyl) phenylethynyl group, 4- (cyclohexylsulfanylpropyl) phenylethynyl Group, 5- (methylsulfanylpropyl) thienyl group, 5- (2-n-hexylsulfanylethyl) thienylethynyl group, 5- (3-n-decylsulfanylpropyl) thienylethynyl group, 5- (cyclohexylsulfanylpropyl) thienyl An alkylsulfanyl or alkylsulfanylalkylaryleneethynyl group such as an ethynyl group;
Ethylaminophenyl group, 4- (3-octylaminopropyl) phenyl group, 4- (3-dodecylaminopropyl) phenyl group, 4- (diethylaminoethyl) phenyl group, 5- (3-octylaminopropyl) thienyl group, Examples thereof include alkylamino or alkylaminoalkylarylene ethynyl groups such as 5- (3-dodecylaminopropyl) thienyl group and 5- (diethylaminoethyl) thienyl group.

Preferred examples of the structure of the compound C of the present invention described above include the compound examples shown in Table 1, but are not limited thereto.

  The obtained compound C can be used as an organic semiconductor material as it is or together with other compounding materials.

〔Composition〕
The compound C of the present invention can be suitably used as an organic semiconductor material as it is or as a composition.
When dissolved in an organic solvent, it can be used as a low-viscosity ink for an organic semiconductor material, and thus is suitable for semiconductor production by a printing method.

  Examples of the organic solvent that can be used include dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, cyclohexanone, acetone, methyl ethyl ketone, ethyl acetate, propyl acetate, n-hexane, cyclohexane, n-octane, n-decane, and n-dodecane. , Dimethylformamide, benzene, toluene, cumene, o-xylene, m-xylene, p-xylene, p-cymene, mesitylene, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,5-dimethyl Anisole, 3,5-dimethoxytoluene, 2,4-dimethylanisole, phenetol, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, 1,5-dimethyltetralin, n-propylbenzene, n- Tylbenzene, n-pentylbenzene, 1,3,5-triethylbenzene, 1,3-dimethoxybenzene, pyridine, nitrobenzene, aniline, N-methylaniline, N, N-diethylaniline, benzonitrile, N-methylpyrrolidone, dimethyl Sulfoxide, 2-fluorotoluene, 3-fluorotoluene, 2,5-difluorotoluene, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 4-fluoro-3-methylanisole, 3-trifluoromethylanisole, Examples include bromobenzene, chlorobenzene, o-dichlorobenzene, trichlorobenzene and the like, but the use is not limited thereto.

The concentration of the organic semiconductor material of the present invention in the prepared liquid composition is preferably 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight.
One kind of organic solvent may be used, but a plurality of kinds of solvents may be mixed and used in order to obtain a desired thin film with high homogeneity.

[Organic thin film semiconductor]
The organic thin film semiconductor of the present invention has a semiconductor layer containing the organic semiconductor material.
Although the said semiconductor layer can be manufactured by well-known and usual manufacturing methods, such as a vacuum evaporation method, a composition can be used as the ink for organic semiconductor materials, and a semiconductor can be formed easily with a printing method.

The semiconductor layer of the present invention preferably forms a thin film by applying a liquid composition containing the organic semiconductor material prepared as described above onto a support.
For example, spin coating method, casting method, dipping method, ink jet method, doctor blade method, screen printing method, offset printing method, letterpress printing method, micro contact printing method, wire bar coating method, spray coating method, dispensing method It is possible to produce a thin film by a known wet film formation method such as. Further, depending on the casting method or the like, it is possible to take a form of a flat crystal or a thick film state.
These thin films, thick films, or crystals can be used not only as a semiconductor layer but also as a charge transporting member for various functional elements such as a photoelectric conversion element, a thin film transistor element, and a light emitting element.

Applicable organic semiconductor devices include diodes, organic transistors, memories, photodiodes, light emitting diodes, light emitting transistors, sensors such as gas sensors, biosensors, blood sensors, immune sensors, artificial retinas, taste sensors, RFID, etc. Is mentioned.

Especially, since the organic-semiconductor material of this invention has a high charge mobility of 0.1 cm < ² > / Vs or more, the application to an organic transistor or a light-emitting device is especially useful. The organic transistor can be suitably used as a switching transistor, a signal driver circuit element, a memory circuit element, a signal processing circuit element, or the like of a pixel constituting the display. Examples of the display include a liquid crystal display, a dispersed liquid crystal display, an electrophoretic display, a particle rotating display element, an electrochromic display, an organic electroluminescence display, and electronic paper.

In addition, an organic transistor usually has a source electrode, a drain electrode and a gate electrode, a gate insulating layer, and an organic semiconductor layer, and there are various types of transistors depending on the arrangement of each electrode and each layer. The organic semiconductor material of the present invention is not limited to the type of transistor, and can be used for any transistor. For the types of transistors, reference can be made to Aldrich Basic Material Science No. 6 “Basics of Organic Transistors”.

(Confirm semiconductor device operation)
As shown in the Examples, it is possible to confirm that the organic semiconductor material of the present invention can be used as an organic transistor by fabricating an FET and evaluating its characteristics.
For details of the semiconductor device operation confirmation by such a method, see, for example, the document S.A. F. Nelson, Y .; -Y. Lin, D.D. J. et al. Gundlach, and T.G. N. Jackson, Temperature-independent transport in high-mobility penentene transistors, Appl. Phys. Lett. , 72, no. 15 1854-1856 (1998).

  Hereinafter, an example is given and explained in detail.

[Example 1] Synthesis of Compound B-1 and Compound C-1 by the production method of the present invention

First, BTBT (15.0 g, 62.4 mmol) was added to dichloromethane (750 mL), and the mixture was stirred until it reached −10 ° C. in a nitrogen gas atmosphere. Next, aluminum chloride (33.6 g, 252.1 mmol) was added, and the temperature was lowered to -70 ° C. After reaching −70 ° C., decanoyl chloride (12.0 g, 63.0 mmol) was added dropwise over 20 minutes and stirred for 3.5 hours. After adding the reaction solution to water (400 g), dichloromethane (200 g) was added and transferred to a separatory funnel. The lower layer was separated and washed twice with water (300 g), and then the organic layer was concentrated. The precipitate was dissolved in toluene (30 g) by heating and then recrystallized at room temperature to obtain 20.9 g of 2- (nonyl-1-one) -BTBT yellow crystals (yield 85%).

Then 2- (nonyl-1-one) -BTBT (20.0 g, 50.6 mmol), 85.5% potassium hydroxide (8.64 g, 131.8 mmol), hydrazine monohydrate (16.0 g, (319.4 mmol) was added to diethylene glycol (760 mL), and the mixture was stirred under a nitrogen atmosphere, heated to 100 ° C., and stirred for 1 hour. Then, it heated up to 170 degreeC, the water | moisture content was removed from the reaction system using the decanter, and it heat-stirred for 4 hours. After cooling to room temperature, the solid matter precipitated in the reaction solution was collected by filtration and washed with water and ethanol in this order. The solid after washing was vacuum-dried at 70 ° C. to obtain 18.8 g of 2-decyl-BTBT (yield 98%).

Further, 15 g (39.46 mmol) of 2-decyl-BTBT was dissolved in 550 mL of chloroform and then cooled to 0 ° C., and 7.88 g (49.32 mmol) of bromine was added dropwise over 20 minutes. The mixture was further stirred at 0 ° C. for 0.5 hour, then warmed to room temperature and stirred for 3 hours to stop the reaction. Water was added for liquid separation, the lower layer was taken, and concentrated to dryness to obtain a crude solid. This solid was recrystallized from acetone to obtain 13.56 g (yield, 75%) of white crystals of 2-decyl-7-bromoBTBT as the halogenated compound B-1.

The obtained halogenated compound B-1 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.02 (sd, 1H, BTBT ring), 7.75 (d, 1H, BTBT ring), 7.71 (d, 1H, BTBT ring), 7. 69 (s, 1H, BTBT ring), 7.52 (dd, 1H, BTBT ring), 7.27 (dd, 1H, BTBT ring), 2.77 (t, 2H, ArCH ₂ ), 1.70 ( _{q, 2H, ArCH 2 CH 2} ), 1.2~1.4 (m, 14H, -CH 2 -), 0.88 (t, 3H, CH 3)

Finally, under nitrogen atmosphere, 2-decyl-7-bromoBTBT (1.23 g, 2.7 mmol) was added to copper iodide (0.11 g, 0.6 mmol), bis (triphenylphosphine) palladium (II) dichloride (0.08 g) 0.1 mmol) and 36 mL of triethylamine were added, and nitrogen gas was bubbled at 25 ° C. for 15 minutes. Under a nitrogen atmosphere, 0.56 g (5.4 mmol) of ethynylbenzene was added, the temperature was raised to 35 ° C., and the mixture was heated and stirred for 30 minutes. Then, after heating up to 85 degreeC, it heated and stirred for 40 hours. After cooling to room temperature, the reaction solution was added to 250 mL of water. Further, the produced solid was washed with 100 mL of acetone. After the solid was dissolved in 500 mL of cyclohexane heated to 50 ° C., 2 g of silica gel and 2 g of a metal scavenger were added to this solution to prepare a slurry. After stirring the slurry at 50 ° C. for 1 hour, the silica gel and the metal scavenger were removed by filtration and recrystallized from the filtrate to obtain 0.84 g (yield, 65%) of white crystals of 2-decyl-7-ethynylbenzene BTBT. %). The reaction step from 2-decyl-BTBT as a starting material to compound C-1 as a target product is two steps, and the yield is 49%.

The obtained compound C-1 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.02 (sd, 1H, BTBT ring), 7.75 (d, 1H, BTBT ring), 7.72 (d, 1H, BTBT ring), 7. 65 (s, 1H, BTBT ring), 7.55 to 7.48 (3H, BTBT ring and phenyl), 7.31 to 7.28 (3H, phenyl), 7.22 (dd, 1H, BTBT ring) _{, 2.77 (t, 2H, ArCH} 2), 1.70 (q, 2H, ArCH 2 CH 2), 1.2~1.4 (m, 14H, -CH 2 -), 0.88 (t , 3H, _-CH 3)

[Example 2] Synthesis of Compound B-1 and Compound C-2 by the production method of the present invention

First, 15 g (39.46 mmol) of 2-decyl-BTBT obtained by the same method as in Example 1 was dissolved in 550 mL of chloroform, cooled to 0 ° C., and 14.9 g (52.0 mmol) of dibromoisocyanuric acid was added. did. After stirring at −0 ° C. for a further 0.5 hour, the temperature was raised to 40 ° C. and stirred for 10 hours to stop the reaction. Water was added and the lower layer was taken and concentrated to dryness to give a crude solid. This solid was recrystallized from acetone to obtain 11.75 g (yield, 65%) of white crystals of 2-decyl-7-bromoBTBT as the halogenated compound B-1.

The obtained halogenated compound B-1 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.02 (sd, 1H, BTBT ring), 7.75 (d, 1H, BTBT ring), 7.71 (d, 1H, BTBT ring), 7. 69 (s, 1H, BTBT ring), 7.52 (dd, 1H, BTBT ring), 7.27 (dd, 1H, BTBT ring), 2.77 (t, 2H, ArCH ₂ ), 1.70 ( _{q, 2H, ArCH 2 CH 2} ), 1.2~1.4 (m, 14H, -CH 2 -), 0.88 (t, 3H, CH 3)

Then, under a nitrogen atmosphere, 1.45 g (3.2 mmol) of 2-decyl-7-bromoBTBT, 1.0 g (4.6 mmol) of potassium phosphate, 0.5 g (4.1 mmol) of phenylboronic acid, 58 mL of dimethyl sulfoxide And nitrogen gas was bubbled at 25 ° C. for 15 minutes. Under a nitrogen atmosphere, 0.3 g of tetrakis (triphenylphosphine) palladium was added, the temperature was raised to 80 ° C., and the mixture was heated and stirred for 5 hours. After the reaction solution was cooled to room temperature, it was added to 375 mL of water to prepare a suspension, and 100 mL of chloroform was added to this suspension to prepare a mixed solution. After the mixture was transferred to a separatory funnel, the chloroform layer was washed 3 times with 100 mL of water. 3 g of magnesium sulfate was added to the chloroform layer, stirred at room temperature for 1 hour, dried, and then concentrated to obtain a solid. This solid was dissolved in 500 mL of cyclohexane heated to 50 ° C., and 2 g of silica gel and 2 g of a metal scavenger were added to this solution to prepare a slurry. After stirring the slurry at 50 ° C. for 1 hour, the silica gel and the metal scavenger were removed by filtration and recrystallized from the filtrate to give Compound C-2 as white crystals of 2-decyl-7-phenylBTBT, 0.94 g (Yield, 65%) was obtained. The reaction step from 2-decyl-BTBT as a starting material to compound C-2 as a target product is two steps, and the yield is 42%.

The obtained compound C-2 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.12 (sd, 1H, BTBT ring), 7.92 (d, 1H, BTBT ring), 7.79 (d, 1H, BTBT ring), 7. 73 (s, 1H, BTBT ring), 7.69-7.59 (7H, BTBT ring and phenyl), 7.45-7.38 (3H, phenyl), 7.29 (dd, 1H, BTBT ring) _{, 2.77 (t, 2H, ArCH} 2), 1.70 (q, 2H, ArCH 2 CH 2), 1.2~1.4 (m, 14H, -CH 2 -), 0.88 (t , 3H, CH ₃ )

(Example 3) Synthesis of compounds B-2 and C-3 by the production method of the present invention

  First, 10 g (44.8 mmol) of 8-bromooctanoic acid was stirred at room temperature under a nitrogen atmosphere, and 0.36 mL (4.5 mmol) of pyridine was added. Furthermore, 6.5 mL (89.6 mmol) of thionyl chloride was added and stirred for 2 hours. Then, pyridine and thionyl chloride were removed by nitrogen bubbling to obtain 9 g (yield 83%) of 8-bromooctanoyl chloride.

Then, BTBT (10.71 g, 44.55 mmol) was added to dichloromethane (450 mL), and the mixture was stirred until it reached −10 ° C. under a nitrogen gas atmosphere. Next, AlCl ₃ (33.6 g, 252.1 mmol) was added, and the temperature was lowered to −70 ° C. After reaching −70 ° C., 8-bromooctanoyl chloride (9.0 g, 44.99 mmol) was added dropwise over 20 minutes and stirred for 4 hours. After adding the reaction solution to water (400 mL), dichloromethane (200 g) was added and transferred to a separatory funnel. The lower layer was separated and washed twice with water (300 mL), and then the organic layer was concentrated. The precipitate was dissolved in toluene (30 g) by heating and then recrystallized at room temperature to obtain 2- (8-bromooctyl-1-one) -BTBT yellow crystals, 11.2 g (yield 56%).

Further, 7.71 g (57.82 mmol) of aluminum chloride and 12.89 g (148.3 mmol) of tert-butylaminoborane were added to dichloromethane (100 mL), and the mixture was stirred until it reached 0 ° C. in a nitrogen atmosphere. A mixture of 450 mL of dichloromethane and 11.0 g (24.7 mmol) of 2- (8-bromooctyl-1-one) -BTBT was added dropwise over 20 minutes, stirred for 30 minutes, warmed to room temperature, and stirred for 3 hours. . After the temperature was lowered to 0 ° C., 500 mL of 0.5 mol / L hydrochloric acid aqueous solution was added to the reaction solution, and then transferred to a separatory funnel. The lower layer was separated and washed twice with water (500 mL), and then the organic layer was concentrated to obtain 10.0 g (yield 94.1%) of 2- (8-bromooctyl) -BTBT as yellow crystals.

Thereafter, 10.0 g (23.18 mmol) of 2- (8-bromooctyl) -BTBT was dissolved in 230 mL of chloroform, cooled to 0 ° C., and 4.62 g (28.97 mmol) of bromine was added. The mixture was further stirred at −0 ° C. for 0.5 hour, then warmed to room temperature and stirred for 10 hours to stop the reaction. Water was added for liquid separation, the lower layer was taken, and concentrated to dryness to obtain a crude solid. This solid was recrystallized from cyclohexane to obtain 7.10 g (yield, 60%) of 2- (8-bromooctyl) -7-bromoBTBT as a halogenated compound B-2.

The obtained halogenated compound B-2 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 7.9 (sd, 1H, BTBT ring), 7.75 (d, 1H, BTBT ring), 7.71 (d, 1H, BTBT ring), 7. 69 (s, 1H, BTBT ring), 7.52 (dd, 1H, BTBT ring), 7.27 (dd, 1H, BTBT _{ring), 3.38 (t, 2H,} -CH 2 -Br), 2 _{.71 (t, 2H, ArCH 2} ), 1.83 (q, 2H, CH 2 CH 2 -Br), 1,67 (q, 2H, ArCH 2 -CH 2 -), 1.2~1 _{.4 (m, 8H, -CH 2} -)

And in nitrogen atmosphere, 2- (8-bromooctyl) -7-bromoBTBT 2.80 g (5.5 mmol), sodium carbonate 2.92 g (27.6 mmol), phenylboronic acid 1.39 g (11.0 mmol) Then, 140 mL of tetrahydrofuran and 30 mL of water were added, and nitrogen gas was bubbled at 25 ° C. for 15 minutes. In a nitrogen atmosphere, 0.56 g of tetrakis (triphenylphosphine) palladium was added, the temperature was raised to 65 ° C., and the mixture was heated and stirred for 16 hours. After the reaction solution was cooled to room temperature, it was added to 500 mL of water to prepare a suspension, and further 100 mL of chloroform was added to this suspension to prepare a mixed solution. After the mixture was transferred to a separatory funnel, the chloroform layer was washed 3 times with 100 mL of water. 3 g of magnesium sulfate was added to the chloroform layer, stirred at room temperature for 1 hour, dried, and then concentrated to obtain a solid. This solid was dissolved in 500 mL of cyclohexane heated to 50 ° C., and 2 g of silica gel and 2 g of a metal scavenger were added to this solution to prepare a slurry. After stirring the slurry at 50 ° C. for 1 hour, the silica gel and the metal scavenger were removed by filtration and recrystallized from the filtrate to obtain 1.81 g of white crystals of 2- (8-bromooctyl) -7-phenylBTBT. Yield, 65%).

  Finally, in a nitrogen atmosphere, 0.2 g (0.40 mmol) of 2- (8-bromooctyl) -7-phenylBTBT, 0.23 g (0.71 mmol) of cesium carbonate, 0.26 g of tetrabutylammonium iodide (0. 71 mmol) was added to 30 mL of tetrahydrofuran and stirred at room temperature. Under nitrogen, 0.30 g (0.71 mmol) of ethyl mercaptan was added and stirred at room temperature for 6 hours. Thereafter, the reaction solution was added to 300 mL of water, and the precipitate was filtered and washed with methanol to obtain a solid. 2- (8- (ethylthio) octyl which becomes compound C-3 by refining 100 mg of this solid substance with silica gel (solvent composition: chloroform / cyclohexane = 10 / 90-50 / 50) and recrystallizing with cyclohexane. 70 mg of) -7-phenyl BTBT was obtained.

The obtained compound C-3 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.12 (sd, 1H, BTBT ring), 7.92 (d, 1H, BTBT ring), 7.79 (d, 1H, BTBT ring), 7. 73 (s, 1H, BTBT ring), 7.69-7.59 (7H, BTBT ring and phenyl), 7.45-7.38 (3H, phenyl), 7.29 (dd, 1H, BTBT ring) _{, 2.77 (t, 2H, ArCH} 2), 2.49~2.56 (4H, -CH 2 -S-CH 2), - 1.70 (q, 2H, ArCH 2 CH 2), 1. _{3~1.6 (m, 14H, -CH 2} -), 1.25 (t, 3H, -S-CH 2 -CH 3)

Example 4 Synthesis of Compound B-3 and Compound C-4 by the Production Method of the Present Invention

First, a solution in which 4.45 g (18.5 mmol) of BTBT obtained by the method described in JP 2010-275192 A, 400 mL of chloroform, and 3.58 g (22.4 mmol) of bromine in 20 mL of chloroform was added, and at room temperature. Reacted for 3 days. Next, 50 mL of a 1% aqueous sodium thiosulfate solution was added to the reaction solution and stirred to separate the organic phase. The organic phase was washed with 50 mL of a saturated aqueous sodium chloride solution, and the organic phase was dried over anhydrous magnesium sulfate, then washed with acetone and filtered to obtain a mixture of 2-bromoBTBT.

Next, 2.6 g (7.5 mmol) of 4-decylphenylboronic acid pinacol, 50 mL of tetrahydrofuran, and 15 mL of a 2 mol / L sodium carbonate aqueous solution were added to 2 g of the mixture of 2-bromoBTBT, and 15 mL of distilled water was added. After substituting with argon for 20 minutes, 0.36 g (0.3 mmol) of tetrakis (triphenylphosphine) palladium was added and reacted at 60 ° C. for 18 hours. After cooling, 400 mL of distilled water was added, the insoluble matter was collected by filtration, washed with water, and further washed with methanol. Further, recrystallization was performed with 180 mL of cyclohexane to obtain 1.4 g (yield 55%) of 2- (4-decylphenyl) BTBT.

Further, 1 g (2.19 mmol) of 2- (4-decylphenyl) BTBT was dissolved in 40 mL of a mixed solvent of chloroform / acetic acid = 1/1, and then cooled to 0 ° C., and 0.82 g (5.24 mmol) of bromine was added for 20 minutes. It was dripped over. The mixture was further stirred at 0 ° C. for 0.5 hour, then warmed to room temperature and stirred for 20 hours to stop the reaction. A 50% 1% aqueous sodium thiosulfate solution was added to separate the layers, the lower layer was taken, and concentrated to dryness to obtain a crude solid. This solid was recrystallized from cyclohexane to obtain 0.64 g (yield, 55%) of white crystals of 2-bromo-7- (4-decylphenyl) BTBT as the halogenated compound B-3.

The obtained halogenated compound B-3 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.11 (s, 1H, BTBT ring), 8.06 (s, 1H, BTBT ring), 7.91 (d, 1H, BTBT ring), 7. 74 (d, 1H, BTBT ring), 7.70 (dd, 1H, BTBT ring), 7.60 (d, 2H, phenyl), 7.56 (dd, 1H, BTBT ring), 7.30 (d , 2H, phenyl), 2.66 (t, 2H, Ar—CH ₂ ), 1.64 (q, 2H, —CH ₂ —), 1.27 (q, 14H, —CH ₂ —), 0. _{88 (t, 3H, -CH 3} )

Finally, 0.35 g (0.65 mmol) of 2- (4-decyl) -phenyl BTBT, 0.0025 g (0.01 mmol) of copper iodide and bis (triphenylphosphine) palladium (II) dichloride in a nitrogen atmosphere. 0075 g (0.02 mmol), diisopropylamine 0.3 mL, and tetrahydrofuran 10 mL were added, and nitrogen gas was bubbled at 25 ° C. for 15 minutes. Under a nitrogen atmosphere, 0.04 mL of 1.5 mol / L tri-t-butylphosphine and 0.14 g (0.78 mmol) of 1-ethynyl-4-pentylbenzene were added, heated to 35 ° C., and heated for 30 minutes. Stir. Then, after heating up to 60 degreeC, it heat-stirred for 40 hours. After cooling to room temperature, the reaction solution was added to 250 mL of water. Further, the produced solid was washed with 100 mL of acetone. After the solid was dissolved in 500 mL of cyclohexane heated to 50 ° C., 2 g of silica gel and 2 g of a metal scavenger were added to this solution to prepare a slurry. After stirring the slurry at 50 ° C. for 1 hour, the silica gel and the metal scavenger were removed by filtration and recrystallized from the filtrate to give 2- (4-decylphenyl) -7 ((4-pentylphenyl) ethynyl) BTBT. 0.23 g (yield, 67%) of white crystals was obtained.

The obtained compound C-4 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.11 (sd, 1H, BTBT ring), 8.09 (s, 1H, BTBT ring), 7.92 (d, 1H, BTBT ring), 7. 83 (d, 1H, BTBT ring), 7.70 (dd, 1H, BTBT ring), 7.62-7.58 (3H, BTBT ring and phenyl), 7.48 (d, 2H, phenyl), 7 .30 (d, 2H, phenyl), 7.19 (d, 2H, _{phenyl), 2.66 (m, 4H,} ArCH 2), 1.64 (m, 4H, -CH 2 -), 1.35 ˜1.28 (m, 18H, —CH ₂ —), 0.89 (, 6H, —CH ₃ )

Comparative Example 1 below was performed by the method described in Patent Document 3.
Comparative Example 1 Synthesis of Compound C-1 by Conventional Production Method First, 4.96 g (13 mmol) of 2-decyl-BTBT obtained by the same method as in Example 1 was dissolved in 320 mL of dichloromethane at −50 ° C. Then, 24 mL of a 1.2 M dichloromethane solution of fuming nitric acid was added dropwise over 30 minutes. After further stirring at −50 ° C. for 2 hours, 26 mL of saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. The lower layer was separated by separation, washed with 10% brine, dried over anhydrous magnesium sulfate and concentrated to dryness to obtain a crude solid. This solid was recrystallized from 2-butanone to obtain yellow crystals of 2-decyl-7-nitroBTBT, 3.72 g (yield, 67%).

Next, 2.56 g (6 mmol) of 2-decyl-7-nitroBTBT and 1.84 g of tin powder were suspended in 30 mL of acetic acid, and 5.4 mL of concentrated hydrochloric acid was slowly added dropwise with stirring and heating at about 70 ° C. Furthermore, after reacting at 100 ° C. for 1 hour, the mixture was cooled to 10 ° C. or lower and the solid was collected by filtration. This solid was dispersed in about 100 mL of chloroform, washed sequentially with concentrated aqueous ammonia and saturated brine, dried over anhydrous magnesium sulfate, and concentrated to dryness to obtain a crude solid. This solid was separated and purified on a silica gel column (chloroform / cyclohexane = 1/1, 1% triethylamine added) and recrystallized from petroleum benzine to give 1.72 g of a fine gray 2-amino-7-decyl BTBT (yield, 72%).

Further, 60 mL of dichloromethane was added to 1.58 g (4 mmol) of 2-amino-7-decyl BTBT, and 864 mg of trifluoroborate ether complex and 504 mg of t-butyl nitrite were added dropwise under cooling at −15 ° C. After raising the reaction temperature to 5 ° C. in about 1 hour, a solution of 1.6 g of iodine, 1.32 g of potassium iodide and 100 mg of tetrabutylammonium iodide in a dichloromethane-THF mixture (1: 2) 12 mL was added. The mixture was reacted for 8 hours under reflux with heating, diluted with chloroform, washed successively with 10% sodium thiosulfate, 5M sodium hydroxide, and 10% brine, dried over anhydrous sodium sulfate, and concentrated to dryness. The obtained dark brown crude solid was purified by a silica gel column (chloroform / cyclohexane = 1/1) and crystallized from chloroform-methanol. Subsequently, recrystallization from ligroin yielded 912 mg of 2-decyl-7-iodoBTBT (yield, 45%).

Finally, 253 mg (0.5 mmol) of 2-decyl-7-iodo BTBT was added to 0.02 g (0.11 mmol) of copper iodide, bis (triphenylphosphine) palladium (II) dichloride under a nitrogen atmosphere. 018 g (0.022 mmol) and 7 mL of triethylamine were added, and nitrogen gas was bubbled at 25 ° C. for 15 minutes. Under a nitrogen atmosphere, ethynylbenzene (0.10 g, 1 mmol) was added, the temperature was raised to 35 ° C., and the mixture was heated and stirred for 30 minutes. Then, after heating up to 85 degreeC, it heated and stirred for 40 hours. After cooling to room temperature, the reaction solution was added to 250 mL of water. Further, the produced solid was washed with 20 mL of acetone. The solid was dissolved in 120 mL of cyclohexane heated to 50 ° C., and 0.5 g of silica gel and 0.5 g of a metal scavenger were added to this solution to prepare a slurry. After stirring the slurry at 50 ° C. for 1 hour, the silica gel and the metal scavenger were removed by filtration, and the crystal was recrystallized from cyclohexane to give white crystals of 2-decyl-7-ethynylbenzene BTBT, 0.16 g (yield) 66%). There are four reaction steps from 2-decyl-BTBT as a starting material to compound C-1 as a target product, and the yield is 14%.

The obtained compound C-1 was analyzed by ¹ H-NMR (300 MHz, CDCl ₃ ).
¹ H-NMR (300 MHz, CDCl ₃ ): δ 8.12 (sd, 1H, BTBT ring), 7.92 (d, 1H, BTBT ring), 7.79 (d, 1H, BTBT ring), 7. 73 (s, 1H, BTBT ring), 7.69-7.59 (7H, BTBT ring and phenyl), 7.45-7.38 (3H, phenyl), 7.29 (dd, 1H, BTBT ring) _{, 2.77 (t, 2H, ArCH} 2), 1.70 (q, 2H, ArCH 2 CH 2), 1.2~1.4 (m, 14H, -CH 2 -), 0.88 (t , 3H, CH ₃ )

  From a comparison between Example 2 and Comparative Example 1, in order to obtain Compound C-1 using 2-decyl-BTBT as a starting material, the yield was 14% in a four-step reaction in the known method. In the production method of the present invention, the reaction could be shortened to two steps, and the yield was greatly improved to 42%.

  The production method of the present invention can produce a compound that can be suitably used as an organic semiconductor material in a high yield.

Claims (4)

A process for producing a halogenated compound B comprising the step of reacting a compound A represented by the following formula (1) with a halogenating agent to obtain a halogenated compound B represented by the formula (2) .

... (1)

... (2)
(In the above formulas (1) and (2), X represents a sulfur atom, an oxygen atom, or a selenium atom,
Ar is an optionally substituted aromatic hydrocarbon or heteroaromatic ring,
R ₁ represents either an alkylene group having 1 to 20 carbon atoms or an alicyclic group,
Y represents O, S, or NH;
R ₂ represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group, or a hydrogen atom,
R ₃ represents a halogen atom,
m and n each independently represents 0 or 1. However, when n is 0, the R ₁ terminal is a hydrogen atom or a halogen atom. )   The production method according to claim 1, wherein X is a sulfur atom. A method for producing compound C, comprising a step of derivatizing halogenated compound B obtained by the production method according to claim 1 or 2 to obtain compound C represented by formula (3).

... (3)
(In the above formula (3), X represents a sulfur atom, an oxygen atom or a selenium atom,
Ar is an optionally substituted aromatic hydrocarbon or heteroaromatic ring,
R ₁ represents either an alkylene group having 1 to 20 carbon atoms or an alicyclic group,
Y represents O, S, or NH;
R ₂ represents an alkyl group having 1 to 20 carbon atoms, an alicyclic group, or a hydrogen atom,
m and n each independently represents 0 or 1. However, when n is 0, the R ₁ terminal is a hydrogen atom or a halogen atom.
R ₄ is an optionally substituted aromatic group, alkenyl group, alkynyl group, or a group represented by the following general formula (4) or (5).

(Ar ₁ is an aromatic hydrocarbon group or heteroaromatic group which may have a substituent, Ar ₂ is an aromatic hydrocarbon group which may have a substituent, R ′ is a hydrogen atom, A trialkylsilyl group having an alkyl group of 4, an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent, * represents a bonding site))   The compound (C) obtained by the manufacturing method of Claim 3.