JP5664897B2 - A method for producing a film-like body containing a π-electron conjugated compound having a benzene ring, and a method for producing the π-electron conjugated compound. - Google Patents

Description

  The present invention is a method for producing a film-like body containing a π-electron conjugated compound containing a benzene ring by removing a specific substituent from a π-electron conjugated compound precursor containing a cyclohexene ring that is easy to synthesize and rich in solubility. , And a method for producing the compound in a simple and high yield, useful in the application in the field of organic electronics, for example, the production of organic electronic devices such as organic electroluminescence (EL) and organic semiconductors, organic solar cells, etc. It is also useful in the production of organic pigments and organic dye films.

  A π-electron conjugated compound having a site in which double bonds and single bonds are alternately arranged has a highly expanded π-electron system, so that it has excellent hole transport and electron transport properties, for example, an electroluminescent material. Organic semiconductor materials (for example, Japanese Patent Application Laid-Open No. 5-05568 of Patent Document 1, WO2006-077788 of Patent Document 2, and Appl. Phys. Lett. 72, p1854 (1998), Non-Patent Document 2; J. Am. Chem. Soc. 128, p12604 <2006)), and organic dyes and organic pigments. As π-electron conjugated materials are widely used in this way, the obstacle is that many of the π-electron conjugated compounds are highly planar and rigid, so the interaction between molecules is extremely strong. In other words, the solubility in water and organic solvents is poor. For example, regarding an organic pigment, dispersion becomes unstable as the pigment aggregates. Taking electroluminescent materials and organic semiconductor materials as an example, they are difficult to apply because they are difficult to dissolve, and there are problems such as the need for vapor deposition such as vacuum deposition. The problem is complicated. Considering a larger area and higher efficiency, there is a demand for adaptability to a wet process by coating by dissolving materials such as spin coat coating, blade coating, gravure printing, inkjet coating, and dip coating in advance. However, the interaction between molecules is very strong, and the adjacency and arrangement between molecules and the tendency to aggregation or crystallization contribute to conductivity. In many cases, the conductivity of the obtained film is incompatible. This is one factor that makes the technology difficult.

  On the other hand, by applying an external stimulus to a precursor into which a reactive substituent that solubilizes an organic compound containing a π-electron conjugated compound is introduced, the substituent is eliminated to obtain the target compound. Methods have been proposed (for example, Japanese Patent Application Laid-Open No. 7-188234 of Patent Document 3, Japanese Patent Application Laid-Open No. 2008-226959 of Patent Document 4, Nature, .388, p131, (1997) of Non-Patent Document 3). In this method, for example, the tBoc group is removed by heating the pigment precursor having a structure in which an amino group or an alcoholic or phenolic hydroxy group in the pigment molecule is modified with a t-butoxycarbonyl group (tBoc group). It is something to be released. However, this method has limited compounds because the substituents need to be linked to nitrogen or oxygen atoms. Furthermore, the improvement was calculated | required also from the viewpoint of the preservability of a precursor.

In recent years, by utilizing the retro Diels-Alder reaction, by applying external stimuli from a precursor having a bulky substituent having high solvent solubility to remove the solubility-imparting group, pentacene, porphyrin compounds, and phthalocyanine compounds can be obtained. The method of conversion is energetically studied. (For example, Japanese Patent Application Laid-Open No. 2007-224019 in Patent Document 5, Japanese Patent Application Laid-Open No. 2008-270843 in Patent Document 6, Adv. Mater., 11, p480 (1999) in Non-Patent Document 4, J Appl.Phys.100, p034502 (2006), Non-Patent Document 6, Appl.Phys.Lett.84, 12, p2085 (2004), Non-Patent Document 7 J.Am.Chem.Soc.126, p1596 (2004) )).
However, among these examples, tetrachlorobenzene molecules and the like are eliminated from the pentacene precursor, but tetrachlorobenzene has a high boiling point and is difficult to remove out of the reaction system, and its toxicity is a concern. Further, both porphyrins and phthalocyanines require complicated synthesis, so the application range is narrow, and the development of substituents that can be synthesized more simply is required.

In addition, there has been proposed a method of converting to a phthalocyanine by detaching the substituent and replacing it with a hydrogen atom by applying an external stimulus to the precursor having a sulfonate ester-based substituent and high solvent solubility. (For example, Japanese Patent Application Laid-Open No. 2009-84555 of Patent Document 8).
However, this method has a problem that the sulfonic acid ester has a high polarity, so that the solubility in a non-polar organic solvent is not sufficient, and the temperature required for the conversion from the precursor is relatively high at 250 ° C to 300 ° C. It was.

  In addition, a method for obtaining an olefin-substituted oligothiophene by solubilizing by introducing a carboxylic acid ester having an alkyl chain at the molecular end of the oligothiophene and desorbing it by applying heat (for example, JP-A-2006-352143 of Patent Document 9 and J. Am. Chem. Soc. 126, p1596 (2004) of Non-Patent Document 7). In this method, desorption occurs by heating at about 150 ° C to 250 ° C, but an olefin group (vinyl group, propenyl group, etc.) is generated at the end of the molecule after conversion, which is accompanied by cis-trans isomerization by heat or light. Therefore, there is a problem that the purity of the material is lowered and the crystallinity is impaired. In addition, the presence of highly reactive terminal olefin groups has a problem in that stability to oxygen and moisture is lowered, and in addition, olefin groups cause a thermal polymerization reaction at high temperatures.

  The present invention has been made in view of the above state of the art, and uses a novel π-electron conjugated compound precursor that has high solubility in organic solvents and is easier to synthesize. An object of the present invention is to provide a production method for obtaining a π-electron conjugated compound containing a benzene ring without generating a chemically unstable terminal olefin group by applying an external stimulus such as heat. Another object of the present invention is to provide an efficient method for producing a continuous thin film of a hardly soluble π-electron conjugated compound by using this technique, and to apply the thin film to an organic electronic device.

The present invention is solved by the following (1) to (11).
(1)
Desorption represented by the following general formulas (IIa) and (IIb) from a coating film formed by applying a coating solution of a solvent containing a π-electron conjugated compound precursor A- (B) m to a substrate. A method for producing a film-like body comprising producing a film-like body containing a π-electron conjugated compound represented by A- (C) m by removing a functional substituent.

(ここでＡはπ電子共役系置換基であり、Ｂは上記一般式(I)で表される構造を少なくとも部分構造として有している溶媒可溶性置換基である。mは自然数である。ただし、Ｂは上記一般式(I)中、(Ｘ_１, Ｘ_２), (Ｙ_１, Ｙ_２)の置換位置の炭素原子を除くＡ上の任意の原子と共有結合を介して連結しているか、Ａ上の(Ｘ_１, Ｘ_２), (Ｙ_１, Ｙ_２)の置換位置の炭素原子を除く任意の炭素原子と縮環している。Ｃは上記一般式（ＩＩ）で表される構造を少なくとも部分構造として有している。
上記一般式(I)および(ＩＩ)中、(Ｘ_１, Ｘ_２）、(Ｙ_１, Ｙ_２)のうち少なくともいずれか一対はともに水素原子であり、残りの一対はともに、ハロゲン原子、置換または無置換の炭素数１以上のアシルオキシ基からなる群から選択される基である。また、(Ｘ_１, Ｘ_２）または(Ｙ_１, Ｙ_２)の一対のハロゲン原子、前記アシルオキシ基は互いに同一であっても異なっていても良く、環状の前記アシルオキシ基を形成していても良い。Ｒ_１乃至Ｒ_４は水素原子、ハロゲン原子または有機基である。
(２)
前記塗工液の塗布が、インクジェット塗布、スピンコート法、溶液キャスト法、ディップコーティング法からなる群から選択される方法により行われることを特徴とする(１)
に記載の膜状体の製造方法。
(３)
前記置換基Ａが、(i) １つ以上の芳香族炭化水素環および芳香族ヘテロ環、若しくは２つ以上の前記環が縮環された化合物、及び、(ii) 前記(i)の環同士が共有結合を介して連結された化合物、からなる群から少なくとも一つ以上選択されるπ電子共役系化合物であることを特徴とする(１)又は(２)に記載の膜状体の製造方法。
(４)
前記化合物Ａ-（Ｂ）mより脱離する成分(Ｘ_１-Ｙ_１およびＸ_２-Ｙ_２）がハロゲン化水素またはカルボン酸を含むことを特徴とする（１）乃至（３）のいずれかに記載の膜状体の製造方法。
(５)
前記化合物Ａ-（Ｂ）mが溶媒可溶性であり、前記脱離性置換基の脱離により生成する前記化合物Ａ-（Ｃ）mが溶媒不溶性であることを特徴とする(２)乃至(４)のいずれかに記載の膜状体の製造方法。
(６)
前記置換基ＢおよびＣが下記一般式（III）および（IV）に示される部分構造を有していることを特徴とする(１)乃至(５)のいずれかに記載の膜状体の製造方法。

(Here, A is a π-electron conjugated substituent, B is a solvent-soluble substituent having at least a partial structure of the structure represented by the above general formula (I), m is a natural number. , B is linked to any atom on A except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) in the above general formula (I) via a covalent bond , A is condensed with any carbon atom except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) on A. C is represented by the above general formula (II) It has a structure as at least a partial structure.
In the above general formulas (I) and (II), at least one of (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) is a hydrogen atom, and the remaining pair is a halogen atom or a substituent. Or, it is a group selected from the group consisting of unsubstituted acyloxy groups having 1 or more carbon atoms. Further, the pair of halogen atoms (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) and the acyloxy group may be the same or different from each other, and may form the cyclic acyloxy group. good. R _{1 to} R ₄ are a hydrogen atom, a halogen atom or an organic group.
(2)
The coating solution is applied by a method selected from the group consisting of inkjet coating, spin coating, solution casting, and dip coating (1)
The manufacturing method of the film-like body as described in 2.
(3)
The substituent A includes (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound in which two or more rings are condensed, and (ii) the rings of (i) The method for producing a film-like body according to (1) or (2), wherein is a π-electron conjugated compound selected from the group consisting of compounds linked by a covalent bond .
(4)
Any of (1) to (3), wherein the components (X ₁ -Y ₁ and X ₂ -Y ₂ ) desorbed from the compound A- (B) m contain a hydrogen halide or a carboxylic acid. The manufacturing method of the film-like body as described in 2.
(5)
(2) to (4), wherein the compound A- (B) m is solvent-soluble and the compound A- (C) m produced by elimination of the leaving substituent is insoluble in the solvent. The method for producing a film-like body according to any one of the above.
(6)
The production of the film-like body according to any one of (1) to (5), wherein the substituents B and C have a partial structure represented by the following general formulas (III) and (IV): Method.

（ここで、Ｘ_１，Ｘ_２，Ｙ_１，Ｙ_２及びＲ_１〜Ｒ_４は前記意味の置換基を表わす）
(７)
π電子共役系化合物前駆体A-(B)mより、下記一般式(ＩＩa)および(ＩＩb)で示される脱離性置換基を脱離させA-(C) mで示されるπ電子共役系化合物を生成することを特徴とするπ電子共役系化合物の製造方法。

(Here, X ₁ , X ₂ , Y ₁ , Y ₂ and R _{1 to} R ₄ represent substituents having the above meanings)
(7)
From the π-electron conjugated compound precursor A- (B) m, the detachable substituent represented by the following general formulas (IIa) and (IIb) is eliminated, and the π-electron conjugated system represented by A- (C) m A method for producing a π-electron conjugated compound, characterized by producing a compound.

(ここでＡはπ電子共役系置換基であり、Ｂは上記一般式(I)で表される構造を少なくとも部分構造として有している溶媒可溶性置換基である。mは自然数である。
ただし、Ｂは上記一般式(I)中、(Ｘ_１, Ｘ_２), (Ｙ_１, Ｙ_２)の置換位置の炭素原子を除くＡ上の任意の原子と共有結合を介して連結しているか、Ａ上の(Ｘ_１, Ｘ_２), (Ｙ_１, Ｙ_２)の置換位置の炭素原子を除く任意の炭素原子と縮環している。Ｃは上記一般式（ＩＩ）で表される構造を少なくとも部分構造として有している。
上記一般式(I)および(ＩＩ)中、(Ｘ_１, Ｘ_２）、(Ｙ_１, Ｙ_２)のうち少なくともいずれか一対はともに水素原子であり、残りの一対はともに、ハロゲン原子、置換または無置換の炭素数１以上のアシルオキシ基からなる群から選択される基である。また、(Ｘ1, Ｘ2）または(Ｙ_１, Ｙ_２)の一対のハロゲン原子、前記アシルオキシ基は互いに同一であっても異なっていても良く、環状の前記アシルオキシ基を形成していても良い。Ｒ_１乃至Ｒ4は水素原子、ハロゲン原子または有機基である。
(８)
前記置換基Aが、(i) １つ以上の芳香族炭化水素環および芳香族ヘテロ環、若しくは２つ以上の前記環が縮環された化合物、及び、(ii)前記(i)の環同士が共有結合を介して連結された化合物、からなる群から少なくとも一つ以上選択されるπ電子共役系化合物であることを特徴とする(７)に記載のπ電子共役系化合物の製造方法。
(９)
前記化合物Ａ-(Ｂ)mが溶媒可溶性であり、前記脱離性置換基の脱離により生成する前記化合物Ａ-(Ｃ)mが溶媒不溶性であることを特徴とする(７)または(８)に記載のπ電子共役系化合物の製造方法。
(１０)
前記置換基ＢおよびＣが下記一般式（III）および（IV）に示される部分構造を有していることを特徴とする(７)乃至(９)のいずれかに記載のπ電子共役系化合物の製造方法。

(Here, A is a π-electron conjugated substituent, B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I), and m is a natural number.
However, B is linked to any atom on A except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) in the above general formula (I) via a covalent bond. Or condensed with any carbon atom except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) on A. C has at least a partial structure of the structure represented by the general formula (II).
In the above general formulas (I) and (II), at least one of (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) is a hydrogen atom, and the remaining pair is a halogen atom or a substituent. Or, it is a group selected from the group consisting of unsubstituted acyloxy groups having 1 or more carbon atoms. Furthermore, (X1, X2) or (Y _1, Y ₂₎ a pair of halogen atoms, the acyloxy groups may be the same or different from each other, they may form the acyloxy group of cyclic. R _{1 to} R 4 are a hydrogen atom, a halogen atom or an organic group.
(8)
The substituent A is (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound in which two or more rings are condensed, and (ii) the rings of (i) (7) The method for producing a π-electron conjugated compound according to (7), wherein at least one π-electron conjugated compound is selected from the group consisting of compounds linked via a covalent bond.
(9)
(7) or (8), wherein the compound A- (B) m is soluble in a solvent, and the compound A- (C) m produced by elimination of the leaving substituent is insoluble in a solvent. ). The manufacturing method of the pi-electron conjugated compound as described in above.
(10)
The π electron conjugated compound according to any one of (7) to (9), wherein the substituents B and C have a partial structure represented by the following general formulas (III) and (IV): Manufacturing method.

（ここで、Ｘ_１，Ｘ_２，Ｙ_１，Ｙ_２及びＲ_１〜Ｒ_４は前記意味の置換基を表わす）
(１１)
(７)乃至（１０）のいずれかに記載の方法で製造されたものであることを特徴とする前記π電子共役化合物系化合物。

(Here, X ₁ , X ₂ , Y ₁ , Y ₂ and R _{1 to} R ₄ represent substituents having the above meanings)
(11)
(7) The π-electron conjugated compound compound produced by the method according to any one of (10) to (10).

According to the production method of the present invention, since a precursor of a solvent-soluble π-electron conjugated compound is used as a raw material, it can be suitably applied to a solution process, and additionally, external stimuli such as heat and light are given. Thus, by removing the substituent imparting solvent solubility, a π-electron conjugated compound containing a benzene ring can be easily produced in high yield without the presence of unstable terminal substituents. Can do. In addition, by using this technique, a thin film containing a π-electron conjugated compound having high purity and excellent characteristics and the compound can be efficiently produced.

It is IR spectrum of the compound 11 in this invention (a horizontal axis is a wave number and a vertical axis | shaft is a transmittance | permeability). It is a TG-DTA spectrum chart of the compound 11 in this invention, a horizontal axis shows temperature [degreeC], the vertical axis left shows weight change [mg], and the vertical axis shows differential heat [mV]. It is the schematic of the organic thin-film transistor of this invention.

  Hereinafter, the present invention will be described with reference to embodiments. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist thereof.

[π-Electron Conjugated Compound Precursor, Film-like Material Obtained by Production Method of the Present Invention, and π-Electron Conjugated Compound]
In the method for producing a film-like body and a π-electron conjugated compound of the present invention, an external stimulus is applied to a “π-electron conjugated compound precursor” having a specific solvent-soluble substituent, and the specific substituent is eliminated. Thus, it is a feature that a desired film-like body and a π-electron conjugated compound are produced. The “π-electron conjugated compound precursor” is represented by A- (B) m. That is, in the formula, A is a π-electron conjugated substituent, B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I), and m is a natural number. However, B is linked to any atom on A except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) in the above general formula (I) through a covalent bond. Or fused to any carbon atom except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) on A.
By applying an external stimulus to this, the solvent-soluble substituent B converts the specific leaving substituents (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) into the form of X ₁ Y ₁ and X ₂ Y ₂ . A compound film-like body represented by the π-electron conjugated compound A- (C) m of the general formula (II), which is desorbed and converted into a substituent C in which a part of the benzene ring is substituted. As well as the compound.
The π-electron conjugated compound precursor used in the present invention has a structure in which a solvent-soluble substituent B is bonded to A, which is a π-electron conjugated substituent.
Here, the solvent-soluble substituent B and the substituent C are represented by the following general formulas (I) and (II).

In the above general formulas (I) and (II), at least one of (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) is a hydrogen atom, and the remaining pair is a halogen atom or a substituent. Or, it is a group selected from the group consisting of unsubstituted acyloxy groups having 1 or more carbon atoms. The pair of halogen atoms (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) and the acyloxy group may be the same or different from each other, and may form the cyclic acyloxy group. Good. R _{1 to} R ₄ are a hydrogen atom, a halogen atom or an organic group.

Examples of the detachable substituent represented by (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) include a hydrogen atom, a halogen atom, and a substituted or unsubstituted acyloxy group having 1 or more carbon atoms. Preferred are a hydrogen atom and a substituted or unsubstituted acyloxy group having 1 or more carbon atoms.

Examples of the substituted or unsubstituted acyloxy group include a formyloxy group, a linear or cyclic aliphatic carboxylic acid and carbonic acid half ester which may contain a halogen atom having 2 or more carbon atoms, and an aromatic carboxylic acid having 4 or more carbon atoms. And acyloxy groups derived from carboxylic acids and carbonic acid half esters. Specifically, for example, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, pentanoyloxy group, hexanoyloxy group, lauroyloxy group, stearoyloxy group, chloroacetoxy group , Fluoroacetoxy group, trifluoroacetyloxy group, 3, 3, 3-trifluoropropionyloxy group, pentafluoropropionyloxy group, cyclopropanoyloxy group, cyclobutanoyloxy group, cyclohexanoyloxy group, benzoyloxy group , P-methoxyphenylcarbonyloxy group, pentafluorobenzoyloxy group and the like.
In addition, carbonic acid esters derived from a carbonic acid half ester corresponding to a structure in which an oxygen atom is inserted between the carbonyl group of the acyloxy group and the alkyl group or aryl group exemplified above can also be mentioned.

Examples of the substituent represented by R _{1 to} R ₅ in the general formulas (I) to (IV) include a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [ A linear or branched or cyclic substituted or unsubstituted alkyl group is represented. These are alkyl groups (preferably substituted or unsubstituted alkyl groups having 1 or more carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group Group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group), cycloalkyl group (preferably substituted or unsubstituted A substituted alkyl group having 3 or more carbon atoms, such as a cyclopentyl group, a cyclobutyl group, Cyclohexyl group, pentafluorocyclohexyl group). In the substituents described below, the alkyl group represents an alkyl group of the above concept],

  Alkenyl group [represents a linear or branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 or more carbon atoms, wherein any one of the above-mentioned alkyl groups having 2 or more carbon atoms has one or more double bonds) For example, ethenyl group (vinyl group), propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 1-octenyl group, 2-octenyl group, 3- An octenyl group, a 4-octenyl group, a 1,1,1-trifluoro-2-butenyl group), a cycloalkenyl group (one or two arbitrary carbon-carbon single bonds of the cycloalkyl group having 2 or more carbon atoms described above) As a double bond For example, 1-cycloallyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3- A cyclohexenyl group, a 1-cycloheptenyl group, a 2-cycloheptenyl group, a 3-cycloheptenyl group, a 4-cycloheptenyl group, a 3-fluoro-1-cyclohexenyl group, etc. The alkenyl group includes a trans (E) isomer and When a stereoisomer such as a cis (Z) isomer exists, any of them may be used, or a mixture of any ratio thereof may be used]

  An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 or more carbon atoms, wherein one or more triple bonds of any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms is mentioned. For example, ethynyl group, propargyl group, trimethylsilylethynyl group, triisopropylsilylethynyl group)

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 or more carbon atoms, such as phenyl, o-tolyl, m-tolyl, p-tolyl, p-chlorophenyl, p-fluorophenyl, p-trifluorophenyl; , Naphthyl and the like),

  A heteroaryl group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound such as 2-furyl, 2-thienyl, 3-thienyl, 2-thienothienyl, -2-benzothienyl 2-pyrimidyl and the like),

  An alkoxyl group and a thioalkoxyl group (preferably a substituted or unsubstituted alkoxyl group and a thioalkoxyl group, and an alkoxy group by inserting an oxygen atom or a sulfur atom at the bonding position of the alkyl group, alkenyl group and alkynyl group exemplified above) A specific example is a thioalkoxy group).

  Aryloxy group and thioaryloxy group [preferably a substituted or unsubstituted aryloxy group and arylthiooxy group, wherein an oxygen atom or a sulfur atom is inserted into the binding site of the aryl group exemplified above, Specific examples include thioalkoxy groups],

  A heteroaryloxy group and a heterothioaryloxy group (preferably a substituted or unsubstituted heteroaryloxy group and heteroarylthiooxy group, wherein an oxygen atom or a sulfur atom is inserted into the binding site of the heteroaryl group exemplified above; Specific examples include heteroaryloxy groups or heteroarylthioaryloxy groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, thiol groups,

  Amino group [preferably amino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted anilino group such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenyl Amino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group such as formylamino, acetylamino, pivaloylamino group, lauroylamino, benzoylamino Group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (preferably a carbon-substituted or unsubstituted aminocarbonylamino group such as carbamoylamino group, N, N-dimethyl group) Aminocarbonyl Amino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group) and the like.

In the general formulas (I) and (III), the acyloxy group (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) preferably has a structure represented by the following general formula (V).

n=1の時は下記一般式(V-1)のような構造となり、(Ｘ₁, Ｘ₂）または (Ｙ₁, Ｙ₂)は環を形成しておらず、それぞれ独立している。

When n = 1, the structure is as shown in the following general formula (V-1), and (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) do not form a ring and are independent of each other.

n=2の時は下記一般式(V-2)のような構造となり、(Ｘ₁, Ｘ₂）または (Ｙ₁, Ｙ₂)の位置で置換され、環を形成している。

When n = 2, the structure is as shown in the following general formula (V-2), and is substituted at the position of (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) to form a ring.

前記Ｒ₅の範囲は前述の通りであるが、その中においても水素原子(一般式(V)でｎ＝２のときは除く)、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアルコキシル基、置換または無置換のチオアルキル基、置換または無置換のアリール基、置換または無置換のヘテロアリール基、シアノ基が特に好ましく、より好ましくは水素原子(一般式（Ｖ）でｎ＝２の時は除く)、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換のチオアルキル基である。最も好ましくは、置換または無置換のアルキル基、置換または無置換のアルコキシル基のときである。

Wherein at range R ₅ are as defined above, (except when the formula (V) in n = 2) a hydrogen atom in, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group A substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted thioalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a cyano group are particularly preferred and more preferred. Is a hydrogen atom (except when n = 2 in formula (V)), a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, or a substituted or unsubstituted thioalkyl group. Most preferably, it is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxyl group.

The leaving components X ₁ -Y ₁ and X ₂ -Y ₂ include, in addition to the halogen atom, the corresponding carboxylic acid in which the —O— bonding site of the substituent constituting the acyloxy group is cleaved and hydrogen is substituted at the terminal. (For example, formic acid, acetic acid, pyruvic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, lauric acid, stearic acid, monochloroacetic acid, monofluoroacetic acid, difluoroacetic acid, 2,2-difluoropropionic acid, trifluoroacetic acid, 3,3,3-trifluoropropionic acid, pentafluoropropionic acid, cyclopropanoic acid, cyclobutanoic acid, cyclohexane acid, benzoic acid, p-methoxybenzoic acid, pentafluorobenzoic acid Acid, methyl hydrogen carbonate, ethyl hydrogen carbonate, isopropyl hydrogen carbonate And carbonic acid half-esters are usually unstable and can be decomposed to the corresponding alcohols (eg, methanol, ethanol, 2-propanol, hexanol) and carbon dioxide. )

The substituent R ₅ in the general formula (V) is not particularly limited, but from the viewpoint of solvent solubility and film formation, the intermolecular interaction as a substituent is reduced to some extent and the affinity with the solvent is increased. However, if the volume change before and after the elimination of the substituent is too great, there is a concern that the thin film may have a problem in the uniformity of the elimination reaction. It is preferable that the substituent is as small as possible while maintaining. In addition, although it is not yet known, it is eliminated that it is an electron-withdrawing substituent (for example, an alkyl group having a halogen, a group having a nitro group, or a cyano group) so that the degree of polarization of carbonyl oxygen is increased. It is considered preferable in terms of efficiency of the reaction.

The π-electron conjugated compound precursor A- (B) m used in the production method of the present invention is composed of the π-electron conjugated substituent A and the solvent-soluble substituent B as described above. In (I), (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) are bonded to any atom on A except the carbon atom at the substitution position via a covalent bond, or (X ₁ , X ₂ ), and (Y ₁ , Y ₂ ) are fused with any carbon atom except the carbon atom at the substitution position.
In the film-like body containing the π-electron conjugated compound of the present invention and the method for producing the compound, the specific compound (X ₁ Y ₁ , X ₂ Y ₂ ) is removed from the solvent-soluble substituent B of the precursor. The π-electron conjugated compound A- (C) m is obtained by separating it and converting it to a substituent C having a benzene ring.
In the present invention, “solvent soluble” means that the solvent has a solubility of 0.05 wt% or more in a state where the solvent is heated to reflux and then cooled to room temperature. Preferably it is 0.1 wt% or more, More preferably, it is 0.5 wt%, Most preferably, it is 1.0 wt% or more.
Further, depending on the combination of the substituents A and B, the solubility of the π-electron conjugated compound A- (C) n in the solvent changes.
Here, “solvent insolubilization” refers to lowering the solubility by one digit or more than the solvent-soluble state. Specifically, it is preferable to lower the solubility from 0.05 wt% or more (solvent solubility) to 0.005 wt% or less in a state where the solvent is heated to reflux and then cooled to room temperature. It is more preferable to reduce the solubility from a solubility of not less than 1% (solvent solubility) to 0.01 wt% or less, and it is particularly preferable to reduce the solubility from a solubility of 0.5 wt% or more (solvent solubility) to less than 0.05 wt%. It is preferable to reduce the solubility from 1.0 wt% or more to less than 0.1 wt%. The term “solvent insoluble” means that the solvent has a solubility of less than 0.01 wt% when the solvent is heated to reflux and then cooled to room temperature, preferably 0.005 wt% or less, and 0.001 wt% % Or less is more preferable.
The type of the solvent used when defining the degree of “solvent soluble” and “solvent insoluble” is not particularly limited, and may be determined depending on the actual solvent and temperature used. 25 ° C.). However, the solvent used in the present invention is not limited thereto.
Since the solubility greatly changes before and after conversion by the elimination reaction, it becomes difficult to be affected by the solvent used at the time of stacking different films, so that organic transistors, organic EL, organic solar cells, etc. It is useful in the manufacturing process of such an organic electronic device.

The π-electron conjugated substituent A may be any as long as it has a π-electron conjugated plane, and specifically includes a benzene ring, a thiophene ring, a pyridine ring, a benzene ring, a pyridine ring, and a pyrazine. A ring, a pyrimidine ring, a triazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a furan ring, a thiophene ring, a selenophene ring, and a silole ring, and more preferably (i) one or more. The aromatic hydrocarbon ring and aromatic heterocycle of the above, or a compound in which the rings are condensed, (ii) a compound in which the rings of (i) are linked via a covalent bond, (i) and ( A π-electron conjugated compound selected from a combination selected from at least one group selected from ii) is preferred, and an aromatic hydrocarbon ring or an aromatic heterocycle thereof is selected. Ring π electrons with each is preferably a non-localized structures throughout fused or linked rings by the interaction by connecting through a condensed ring and covalent.
The number of aromatic hydrocarbon rings or aromatic heterocycles connected by a condensed ring or a covalent bond is preferably 2 or more. Specifically, naphthalene, anthracene, tetracene, chrysene, pyrene, pentacene, thienothiophene, thienozi Thiophene, triphenylene, hexabenzocoronene, benzothiophene, benzodithiophene, [1] benzothieno [3,2-b] [1] benzothiophene (BTBT), dinaphtho [2, 3-b: 2 ', 3'-f ] [3,2-b] condensed polycyclic compounds such as thienothiophene (DNTT), benzodithienothiophene (TTPTT), aromatic carbonization such as biphenyl, terphenyl, quarterphenyl, bithiophene, terthiophene, quarterthiophene Examples thereof include oligomers of hydrogen rings and aromatic heterocycles, phthalocyanines, porphyrins and the like.

  The solvent-soluble substituent B is not particularly limited as long as it partially contains the cyclohexene ring structure represented by the general formula (I), and examples thereof include the following structures.

These are linked to the π-electron conjugated substituent A through a condensed ring or a covalent bond, except for carbon atoms at the substitution positions of R _{1 to} R ₄ and (X ₁ , X ₂ ), (Y ₁ , Y ₂ ). Can be done.

  Examples of the specific structure of A- (B) m that can be obtained by combining the above-described π-electron conjugated substituent A and the solvent-soluble substituent B include the following compound groups. The precursor is not limited to these. Moreover, it can be easily guessed that the solvent-soluble substituent B has a plurality of isomers having different steric configurations of acyloxy groups, and it is presumed that the following compounds are a mixture thereof.

A film containing a π-electron conjugated compound A- (C) m by causing energy to be applied to the precursor A- (B) m, causing a desorption reaction described later, and desorbing a specific substituent. A state body and this compound can be obtained.
Specific examples of A- (C) m (referred to as a specific compound) produced from A- (B) m shown in the above specific examples are shown below. It is not limited to.

[2. Method for producing π-electron conjugated compound by elimination reaction of π-electron conjugated compound precursor]
Since the core part in the method for producing a film-like body containing a π-electron conjugated compound of the present invention can be said to be the production of the π-electron conjugated compound by the elimination reaction, the elimination reaction will be described in detail.
In the case of the production method of the present invention, it is contained in a precursor-containing film formed by coating, for example, on a substrate (support) such as plastics, metal, silicon wafer, glass, etc., and represented by the following general formula (I) From this, the compound (precursor) having a cyclohexene ring structure is desorbed from the elimination components represented by the general formulas (IIa) and (IIb), and converted into a compound having the structure represented by the general formula (II).

In the compound represented by the general formula (I), there are a plurality of stereoisomers having different steric arrangements of substituents. It remains the same. However, X ₁ and Y ₁ and X ₂ and Y ₂ are in the same side with respect to the cyclohexane ring plane, that is, taking a cis structure, the efficiency of the elimination reaction, the conversion temperature, the reaction yield More preferable from the viewpoint.

(X ₁ , X ₂ ), (Y ₁ , Y ₂ ) which are groups leaving from compound (I) are defined as leaving groups, and X ₁ -Y ₁ and X ₂ -Y ₂ are leaving components Is defined. The desorbing component can take the three states of solid, liquid, and gas, but considering the removal to the outside of the system, the desorbing component is preferably liquid or gas, particularly preferably at room temperature or It becomes a gas at the temperature at which the elimination reaction is performed. The boiling point is preferably 500 ° C. or lower at atmospheric pressure (1013 hPa), and is 400 ° C. or lower in view of the ease of removal out of the system and the decomposition / sublimation temperature of the π-electron conjugated compound formed. Is more preferable, and particularly preferably 300 ° C. or lower. In the following, (X ₁ , X ₂ ) is the same acyloxy group, (Y ₁ , Y ₂ ) and R _{1 to} R ₄ are hydrogen atoms, R ₆ is a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy group However, the production examples of the present invention are not necessarily limited thereto.

  In the case of the above example, the carboxylic acid having an alkyl chain represented by the general formula (X) as a leaving component is eliminated from the cyclohexene ring structure represented by the general formula (VIII), and the benzene represented by the general formula (IX) Converted to a structure containing a ring. Also, when R6 is a substituted or unsubstituted alkoxy group, the carbonic acid half ester (X) is unstable, so it decomposes into alcohol (X-1) and carbon dioxide (X-2) as shown below. May be.

上記一般式(VIII)で示される化合物から脱離成分が脱離する機構について以下に概略を示す。

An outline of the mechanism by which the elimination component is eliminated from the compound represented by the general formula (VIII) will be described below.

As shown in the above general formula (XI), by taking a six-membered cyclic transition state, the hydrogen atom on the β-carbon undergoes 1,5-rearrangement onto the oxygen atom of the carbonyl, resulting in concerted elimination. The reaction occurs, the carboxylic acid is eliminated, and the cyclohexene ring structure is converted to a benzene ring structure as shown in the general formula (VIII). Even when there are a plurality of stereoisomers, the reaction proceeds as described above, although the reaction rate is different as described above.
However, it is more preferable from the viewpoint of elimination reaction efficiency, conversion temperature, and reaction yield that the acyloxy group and the hydrogen atom are on the same side of the cyclohexane ring plane, that is, has a cis structure.

  Here, the hydrogen atom on the β carbon can be extracted not only by the oxygen atom, but also in a compound substituted with a chalcogen atom such as selenium, tellurium, polonium or the like, which is also a group 16 element. obtain. Although the details are not yet clear, the greater the degree of polarization of the atoms to δ-, the greater the force withdrawing hydrogen atoms, which may reduce the energy required to cause the elimination reaction.

  Examples of the energy applied to perform the elimination reaction include heat, light, electromagnetic waves, and acid bases. From the viewpoints of reactivity, yield, and post-treatment, thermal energy or light energy is desirable, and thermal energy is particularly desirable. preferable. It is also possible to use both heat and light. When used together, they may be used simultaneously or before and after. Moreover, you may apply the said energy in presence of an acid or a base.

  Usually, the elimination reaction depends on the structure of the functional group, but often requires heating. The heating method for carrying out the elimination reaction includes a method of heating on a support, a method of heating in an oven, a method of irradiation with microwaves, a method of heating by converting light into heat using a laser, Although various methods, such as using a photothermal conversion layer, can be used, it is not limited to these.

As for the heating temperature for carrying out the elimination reaction, it is possible to use a range of room temperature (approximately 25 ° C.) to 500 ° C. The lower limit temperature is the upper limit temperature considering the thermal stability of the material and the boiling point of the elimination component. In consideration of energy efficiency, the abundance of unconverted molecules, decomposition of the π-electron conjugated compound after conversion, etc., the range of 40-500 ℃ is preferable. Furthermore, the thermal stability of the precursor synthesis and the π electron after conversion Considering the decomposition of the conjugated compound and the sublimation temperature, it is more preferably in the range of 80 ° C to 400 ° C, particularly preferably in the range of 80 ° C to 300 ° C.
Here, the sublimation temperature can be defined as a temperature at which a weight loss of 5%, preferably 3%, more preferably 1.0%, from the initial weight is observed in TG-DTA, for example.
Regarding the heating time, the higher the temperature, the shorter the reaction time, and the lower the temperature, the longer the time required for the elimination reaction. Further, although depending on the reactivity and amount of the precursor, it is usually 0.5 to 120 minutes, preferably 1 to 60 minutes, particularly preferably 1 minute to 30 minutes.

  When light is used as an external stimulus, an infrared lamp, irradiation with light having a wavelength absorbed by the compound (for example, exposure to a wavelength of 405 nm or less), and the like may be used. At that time, a semiconductor laser may be used. For example, near-infrared laser light (usually laser light having a wavelength of around 780 nm), visible laser light (usually laser light having a wavelength in the range of 630 nm to 680 nm), and laser light having a wavelength of 390 to 440 nm can be mentioned. Laser light having a wavelength of 390 to 440 nm is particularly preferable, and semiconductor laser light having an oscillation wavelength in the range of 440 nm or less is preferably used. Among them, as a preferable light source, a blue-violet semiconductor laser light having an oscillation wavelength in the range of 390 to 440 (more preferably 390 to 415 nm) and an infrared semiconductor laser light having a central oscillation wavelength of 850 nm are half wavelength using an optical waveguide device. And blue-violet SHG laser light having a central oscillation wavelength of 425 nm.

  The above acid or base acts as a catalyst for elimination reaction, and conversion at a lower temperature is possible. Although there is no particular limitation on the method of using these, they may be added as they are, they may be dissolved in any solvent and added as a solution, or they may be vaporized and subjected to heat treatment in the atmosphere. Alternatively, a photoacid generator, a photobase generator, or the like may be added, and an acid and a base may be obtained in the system by the above-described light irradiation.

  As the acid, 2-butyloctanoic acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, formic acid, phosphoric acid and the like can be used. Particularly preferred are hydrochloric acid, nitric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid, which are volatile and highly acidic.

  Examples of the base include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium hydrogen carbonate, sodium carbonate and potassium carbonate, amines such as triethylamine and pyridine, diazabicycloundecene, diazabicyclononene. Amidines such as can be used.

  Examples of the photoacid generator include ionic generators such as sulfonium salts and iodonium salts and nonionic generators such as ionic photoacid generator imide sulfonate, oxime sulfonate, disulfonyldiazomethane, and nitrobenzyl sulfonate. .

Examples of the photobase generator include carbamates, acyl oximes, ammonium salts and the like.
Of these, it is preferable to carry out the reaction in an atmosphere of a volatile acid or base in view of ease of removal of the acid-base after the reaction.

The atmosphere for the desorption reaction can be carried out in the air with or without the above catalyst. However, in order to eliminate side effects such as oxidation and the influence of moisture, In order to promote exclusion outside the system, it is desirable to carry out in an inert gas atmosphere or under reduced pressure.
Examples of the leaving group include, in addition to the carboxylic acid esters exemplified above, halogen atoms, carbonic acid esters, xanthogenic acid esters, sulfonic acid esters, esters represented by phosphoric acid esters, and amine oxides and sulfoxides having β hydrogen, and Although selenoxide etc. are mentioned, it is not limited to these in particular.

  With respect to the method for forming the above-described leaving group, a method of obtaining carbonate by reacting phosgene with alcohol or reacting alcohol with a carbonic acid half ester such as alkyl chloroformate, alcohol with carboxylic acid chloride or A method of obtaining a carboxylic acid ester by reacting a carboxylic acid anhydride or exchanging a halogen atom with a silver carboxylate or a carboxylic acid quaternary ammonium salt, adding carbon disulfide to an alcohol, and reacting an alkyl iodide with xanthogen Examples include a method for obtaining an acid ester, a method for obtaining an amine oxide by reacting a tertiary amine with hydrogen peroxide or a carboxylic acid, and a method for obtaining an selenoxide by reacting an orthoselenocyanonitrobenzene with an alcohol. is not.

 [3. Method for producing π-electron conjugated compound precursor]

  A method for forming a halogen group and an acyloxy group in the cyclohexene skeleton of the soluble substituent B will be described in detail.

  It can be derived from a compound having a cyclohexene skeleton as shown in the following general formula (XII), which can be produced by a conventionally known method and used as a raw material. Each preferably has one or more hydrogen atoms.

(式中Ｒ₁-Ｒ₄は前記したものと同一の範囲である。)

(Wherein R ₁ -R ₄ are in the same range as described above.)

Subsequently, as shown in the general formula (XIII), the 1,4-position or the 2,3-position is selectively halogenated using a brominating agent, but iodine, bromine, A chlorine atom is preferable, and a bromine atom is particularly preferable. Examples of the brominating agent include N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide and the like, and it is preferable to carry out these in combination with a radical initiator such as azobisisobutyronitrile and benzoyl peroxide. .
A solvent is not necessarily required, but various organic solvents can be used, and benzene, carbon tetrachloride and the like are particularly preferable.

Subsequently, as shown in the general formula (XIV), 2 equivalents of silver carboxylate or carboxylic acid quaternary ammonium salt is allowed to act on the dihalogen obtained in the above reaction, whereby the 1, 4-position or 2, A target product in which the 3-position is acyloxylated can be obtained.
Also, an asymmetric compound can be obtained by allowing each equivalent of different silver carboxylates or carboxylic acid quaternary ammonium salts to act on each equivalent. However, since the reaction rates in the elimination reaction may vary greatly, the carboxylic acids are preferably the same.
Depending on the reaction conditions and the structure of the carboxylic acid used, a plurality of stereoisomers having different steric configurations may be generated. Specifically, the racemic mixture and the meso form may be obtained in an arbitrary ratio depending on the configuration of the acyloxy group bonded to the cyclohexene ring. These can be separated by recrystallization or chromatography using an optically active fixed layer. Examples of the carboxylic acid silver salt include silver acetate, silver trifluoroacetate, silver 3,3,3-trifluoropropionate, and the carboxylic acid quaternary ammonium salt includes tetramethylammonium pentahydrate and the above-mentioned. And salts with carboxylic acids (for example, acetic acid, butyric acid, valeric acid, propionic acid, pivalic acid, caproic acid, stearic acid, trifluoroacetic acid, 3,3,3-trifluoropropionic acid). As the solvent, various organic solvents such as dimethylformamide, dithymer sulfoxide, tetrahydrofuran, acetone, and toluene can be used. In order to prevent reaction rate and side reaction, it is preferable to use a dehydrated solvent.

(式中、Acyはアシル基を示す。式中Ｒ₁〜Ｒ₄は前記したものと同一の範囲である。)

また、炭酸エステル構造を合成するには、原料の関係上、クロロギ酸アルキル等を用いるのが簡便である。その場合、下記一般式(XV)で示されるように上記アシルオキシ化合物を塩基等で加水分解したジオールへと変換することが好ましい。ここで用いるアシル基は加水分解されやすい酢酸エステルやプロピオン酸エステルなどが好ましい。

(In the formula, Acy represents an acyl group. In the formula, R _{1 to} R ₄ are in the same range as described above.)

Moreover, in order to synthesize a carbonate structure, it is convenient to use alkyl chloroformate or the like because of the raw materials. In that case, it is preferable to convert the acyloxy compound into a diol hydrolyzed with a base or the like as represented by the following general formula (XV). The acyl group used here is preferably an acetic acid ester or propionic acid ester which is easily hydrolyzed.

上記、溶媒としては、アルコールやアセトン、ジメチルホルムアミド等が好ましい。塩基としては、水酸化リチウム、水酸化ナトリウムや水酸化カリウム、炭酸カリウム、水素化ナトリウム、ナトリウムメトキシド、カリウムtert-ブトキシドなどの強塩基を用いることが好ましい。反応温度は、副反応を防ぐために、0℃から室温程度が好ましい。

続けて、下記一般式(XVI)に示すように水酸基をアシル化する。

As the solvent, alcohol, acetone, dimethylformamide and the like are preferable. As the base, it is preferable to use a strong base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride, sodium methoxide, potassium tert-butoxide. The reaction temperature is preferably about 0 ° C. to room temperature in order to prevent side reactions.

Subsequently, the hydroxyl group is acylated as shown in the following general formula (XVI).

上記溶媒としては、クロロギ酸アルキルと反応しないもので、基質を良く溶かすものであれば特に限定されないが、例えばテトラヒドロフラン、ピリジン、ジクロロメタン、クロロホルム、トルエンなどが挙げられ、十分に脱水されたものが好ましい。また、反応の際に発生する塩化水素を補足するために塩基は添加することが好ましい。塩基としては、ピリジン、トリエチルアミン、ジイソプロピルアミン、ジイソプロピルエチルアミン、N, N-ジメチルアミノピリジンなどが挙げられる。これらを溶媒として用いることも可能であり、複数組み合わせて用いても良い。第一選択としては、ピリジンまたはトリエチルアミンと、N, N-ジメチルアミノピリジンの組み合わせが好ましい。
クロロギ酸アルキルとしては、クロロギ酸メチル、クロロギ酸エチル、クロロギ酸プロピル、クロロギ酸イソプロピル、クロロギ酸イソブチルなどが挙げられる。
反応温度は、0℃〜室温程度が反応性、選択性の点で好ましい。
このようにして、炭酸エステル構造を形成することができる。

The solvent is not particularly limited as long as it does not react with alkyl chloroformate and dissolves the substrate well, and examples thereof include tetrahydrofuran, pyridine, dichloromethane, chloroform, toluene, and those that are sufficiently dehydrated are preferable. . Further, it is preferable to add a base to supplement hydrogen chloride generated during the reaction. Examples of the base include pyridine, triethylamine, diisopropylamine, diisopropylethylamine, N, N-dimethylaminopyridine and the like. These can also be used as a solvent, and may be used in combination. As a first choice, a combination of pyridine or triethylamine and N, N-dimethylaminopyridine is preferred.
Examples of the alkyl chloroformate include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, and isobutyl chloroformate.
The reaction temperature is preferably about 0 ° C. to room temperature in terms of reactivity and selectivity.
In this way, a carbonate structure can be formed.

The soluble substituents B and A thus obtained can be condensed by various conventionally known methods to synthesize a π-electron conjugated compound precursor A- (B) m.
For example, in the case of pentacene, it can be performed according to the method described in J. Am. CHem Soc., 129, 2007, pp.15752, and in the case of heteroacenes, J. AM. CHEM. SOC. 2007, 129, 2224-2225 and the like.
In the case of phthalocyanines, the ring-forming reaction is described in 1-62 pages of “Phthalocyanine-Chemistry and Functions” (IPC, 1997) edited by Yasuyoshi Shirai and Nagao Kobayashi. This can be performed according to pages 29 to 77 of “Phthalocyanine as a functional pigment” edited by Eiko Okumura (IPC, 2004). In the case of porphyrins, JP 2009-105336 A It is possible to carry out according to the described method.

In addition, as a linking method by covalent bond between the π-electron conjugated substituent A and the solvent-soluble substituent B in the precursor A- (B) m used in the production method of the present invention, a method by Suzuki coupling reaction, Stille cup Various coupling reactions represented by ring reaction method, Kumada coupling reaction, Negishi coupling reaction method, Hiyama coupling reaction method, Sonogashira reaction method, Heck reaction method, Wittig reaction method, etc. The publicly known method performed using it is illustrated. Among these, the method using the Suzuki coupling reaction or the Stille coupling reaction is particularly preferable from the viewpoint of reactivity and yield that the intermediate is easily derivatized. In forming the carbon-carbon double bond, in addition to the above, a method using a Heck reaction, a Wittig reaction, and the like are also preferable. In addition to the above, the Sonogashira reaction is particularly preferable in the formation of a carbon-carbon triple bond.
Hereinafter, examples in which carbon-carbon bonds are connected by Suzuki coupling reaction and Stille coupling reaction will be described.
The reaction is carried out using a combination of a halogen compound represented by the following general formulas (XV) and (XVI) and a trifluorotriflate compound or a boronic acid derivative and an organotin derivative. However, when the compounds represented by the general formulas (XV) and (XVI) are both a halogen compound, a triflate compound, a boronic acid derivative, and an organotin derivative, the coupling reaction does not occur, and thus it is excluded. Further, it is produced by adding a base to the above mixture only in the case of the Suzuki coupling reaction and reacting in the presence of a palladium catalyst.

  (In the above formula (XV), A is the aforementioned π-electron conjugated substituent, D is a halogen atom (representing a chlorine atom, bromine atom or iodine atom), a triflate (trifluoromethanesulfonyl) group, or boronic acid or an ester thereof. Or represents an organotin functional group, where l is a natural number.)

  (In the above formula (XVI), B is the above-mentioned solvent-soluble substituent, D is a halogen atom (representing a chlorine atom, bromine atom or iodine atom), a triflate (trifluoromethanesulfonyl) group, boronic acid, its ester or organic Represents a tin functional group, k is a natural number.)

  In the synthesis method by Suzuki coupling and Stille coupling reaction, iodine, bromine or triflate is preferable from the viewpoint of reactivity among the halogen or triflate in the general formulas (XV) and (XVI).

As the organotin functional group in the general formulas (XV) and (XVI), a derivative having an alkyltin group such as a SnMe ₃ group or a SnBu ₃ group can be used. Further, as the boronic acid derivative, a boronic acid ester synthesized from a halogenated derivative using bis (pinacolato) diboron which is thermally stable and can be easily handled in air may be used in addition to boronic acid.

  As described above, either the substituent A or B may be a halogen and a triflate, or a boronic acid derivative and an organotin derivative. However, in terms of ease of derivatization and reduction of side reactions, the substituent A is preferred. It is often better to use boronic acid derivatives and organotin derivatives.

In the Stille coupling reaction, a base is not particularly required, but in the Suzuki coupling reaction, a base is always required, and relatively weak bases such as Na ₂ CO ₃ and NaHCO ₃ give good results. When affected by steric hindrance or the like, strong bases such as Ba (OH) ₂ , K ₃ PO ₄ , and NaOH are effective. In addition, caustic potash, metal alkoxide, etc., for example, potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, potassium 2-methyl-2-butoxide, sodium 2-methyl-2-butoxide, sodium methoxide, sodium ethoxide, Potassium ethoxide, potassium methoxide, and the like can also be used. An organic base such as triethylamine can also be used.

  Examples of the palladium catalyst include palladium bromide, palladium chloride, palladium iodide, palladium cyanide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate [Pd (acac) 2], diacetate bis (triphenylphosphine) palladium [Pd (OAc) 2 (PPh3) 2], tetrakis (triphenylphosphine) palladium [Pd (PPh3) 4], dichlorobis (acetonitrile) palladium [Pd (CH3CN) 2Cl2], dichlorobis (benzonitrile) palladium [Pd (PhCN) ) 2 Cl2], dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dpppe) Cl2], dichloro [1,1-bis (diphenylphosphino) ferrocene] para Um [Pd (dppf) Cl 2], dichlorobis (tricyclohexylphosphine) palladium [Pd [P (C 6 H 1 1) 3] 2 Cl 2], dichlorobis (triphenylphosphine) palladium [Pd (PPh 3) 2 Cl 2], tris (di Benzylideneacetone) dipalladium [Pd2 (dba) 3], bis (dibenzylideneacetone) palladium [Pd (dba) 2], and the like, such as tetrakis (triphenylphosphine) palladium [Pd (PPh3) 4], dichloro A phosphine-based catalyst such as [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) Cl2], dichlorobis (triphenylphosphine) palladium [Pd (PPh3) 2 Cl2] is preferred.

  In addition to the above, a palladium catalyst synthesized by reaction of a palladium complex and a ligand in the reaction system can be used as the palladium catalyst. Examples of the ligand include triphenylphosphine, trimethylphosphine, triethylphosphine, tris (n-butyl) phosphine, tris (tert-butyl) phosphine, bis (tert-butyl) methylphosphine, tris (i-propyl) phosphine, tris. Cyclohexylphosphine, tris (o-tolyl) phosphine, tris (2-furyl) phosphine, 2-dicyclohexylphosphinobiphenyl, 2-dicyclohexylphosphino-2′-methylbiphenyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6'-triisopropyl-1,1'-biphenyl, 2-dicyclohexylphosphino-2 ', 6'-dimethoxy-1,1'-biphenyl, 2-dicyclohexylphosphino-2'-(N, N'-dimethyl Amino) biphenyl 2-diphenylphosphino-2 ′-(N, N′-dimethylamino) biphenyl, 2- (di-tert-butyl) phosphino-2 ′-(N, N′-dimethylamino) biphenyl, 2- (di- tert-butyl) phosphinobiphenyl, 2- (di-tert-butyl) phosphino-2′-methylbiphenyl, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoethylene, diphenylphosphinoferrocene, Ethylenediamine, N, N ′, N ″, N ′ ″-tetramethylethylenediamine, 2,2′-bipyridyl, 1,3-diphenyldihydroimidazolylidene, 1,3-dimethyldihydroimidazolylidene, diethyldihydroimidazo Lilidene, 1,3-bis (2,4,6- Limethylphenyl) dihydroimidazolylidene and 1,3-bis (2,6-diisopropylphenyl) dihydroimidazolylidene are mentioned, and a palladium catalyst coordinated with any of these ligands is used as a cross-coupling catalyst. Can be used.

  The reaction solvent is preferably one that does not have a functional group capable of reacting with the raw material and that can dissolve the raw material in an appropriate amount. Water, methanol, ethanol, isopropanol, butanol, 2-methoxyethanol 1,2-dimethoxyethane, bis (2-methoxyethyl) ether and other alcohols and ethers, dioxane, tetrahydrofuran and other cyclic ethers, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dimethyl sulfoxide (DMSO) N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. These solvents may be used alone or in combination of two or more. These solvents are preferably dried and degassed in advance.

The temperature of the above reaction is appropriately set depending on the reactivity of the raw materials used and the reaction solvent, and can usually be carried out in the range of 0 ° C to 200 ° C. In either case, the upper limit is below the boiling point of the solvent. It is preferable to suppress. In addition, it is preferable from the viewpoint of yield to keep the temperature below the temperature at which the elimination reaction occurs.
As the lower limit, the reaction can be carried out up to the melting point of the solvent. However, if the temperature is too low, the reaction rate is remarkably lowered, which is not preferable. From the above viewpoint, a range of 0 ° C to 150 ° C is specifically preferable, a range of 0 ° C to 100 ° C is particularly preferable, and a room temperature to 80 ° C is most preferable.
The reaction time in the above reaction can be appropriately set in the reactivity of the raw material used, is preferably 1 to 72 hours, and more preferably 1 to 24 hours.

  The compound obtained as described above is used after removing impurities such as the catalyst used in the reaction, unreacted raw materials, and boronates and organotin derivatives by-produced during the reaction. These purification methods include conventional methods such as reprecipitation, column chromatography, adsorption, extraction (including Soxhlet extraction), ultrafiltration, dialysis, and the use of scavengers to remove the catalyst. Can be used.

In order to make the precursor obtained by the above-described manufacturing method into a thin film, the precursor has sufficient solubility in an organic solvent. Therefore, by selecting an appropriate concentration and viscosity according to the application, a spin coating method can be used. A known film forming method such as a casting method, a dip method, an ink jet method, a doctor blade method, a screen printing method, vacuum deposition, or sputtering can be used. Thereby, it is possible to produce a good thin film excellent in strength, toughness, durability, etc. without cracks. Furthermore, it is possible to remove a soluble substituent from the film of the precursor of the present invention applied by the film forming method to form a film of a π-electron conjugated compound, and a photoelectric conversion element such as an organic solar cell It can be suitably used as a material for various functional elements such as a thin film transistor element and a light emitting element such as an organic EL.

[Electronic device]
The specific compound of this invention can be used for an electronic device, for example. An example of an electronic device is a device that has two or more electrodes, the current flowing between the electrodes and the voltage generated are controlled by electricity, light, magnetism, chemical substances, etc., or the applied voltage or current Thus, a device that generates light, an electric field, or a magnetic field can be used. In addition, for example, an element that controls current or voltage by application of voltage or current, an element that controls voltage or current by application of a magnetic field, an element that controls voltage or current by the action of a chemical substance, or the like can be given. Examples of this control include rectification, switching, amplification, and oscillation.
Corresponding devices currently implemented with inorganic semiconductors such as silicon include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, etc., or these elements Combinations and integrated devices. In addition, a solar cell that generates an electromotive force by light, and an optical element such as a photodiode and a phototransistor that generate a photocurrent can be used.

  An example of an electronic device suitable for applying the specific compound of the present invention is a field effect transistor (FET). Hereinafter, this FET will be described in detail.

"Transistor structure"
3A to 3D are schematic structures of the organic thin film transistor according to the present invention. The organic semiconductor layer (1) of the organic thin film transistor according to the present invention contains the specific compound of the present invention. The organic thin film transistor of the present invention is provided with a gate electrode (4) on a spatially separated source electrode (2), drain electrode (3) and a support (substrate) (not shown),
An insulating film (5) may be provided between the gate electrode (4) and the organic semiconductor layer (1). In the organic thin film transistor, the current flowing in the organic semiconductor layer (1) between the source electrode (2) and the drain electrode (3) is controlled by applying a voltage to the gate electrode (4). The organic thin film transistor of the present invention can be provided on a support, and for example, a commonly used substrate such as glass, silicon, or plastic can be used. In addition, by using a conductive substrate, it can also be used as a gate electrode, and a structure in which a gate electrode and a conductive substrate are stacked can be used. However, the flexibility of a device to which the organic thin film transistor of the present invention is applied. When characteristics such as light weight, low cost, and impact resistance are desired, a plastic sheet is preferably used as the support.
Examples of the plastic sheet include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Is mentioned.

“Film Formation Method: Organic Semiconductor Layer”
The organic semiconductor material according to the present invention can be formed by vapor deposition such as vacuum deposition.
In addition, a thin film can be formed by dissolving the organic semiconductor precursor in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene, and xylene and applying the solution on a support. That is, the solvent for the coating solution containing the precursor A- (B) m can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is 500 ° C. or less. Is preferred. However, the higher the volatility, the better. Those having a boiling point of 50 ° C. or higher are preferred. Although not yet fully confirmed, it may be because conductivity is not only the detachment of the leaving group of the precursor, but also the change of the arrangement state for contact between molecules. In other words, the precursor present in the coating film is removed from the random state and then adjoined, contacted, or regenerated between the molecules by at least a partial change in the direction or position of the molecule from the random state. This may be because it takes time for the arrangement, aggregation, crystallization, and the like to occur.
In any case, specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, and the like having affinity for the polar carboester group as the leaving group of the precursor A- (B) m, ethylene, and the like. Glycols such as glycol, diethylene glycol and propylene glycol, ethers such as tetrahydrofuran (THF) and dioxane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, phenols such as phenol and cresol, dimethylformamide (DMF), pyridine, dimethylamine and triethylamine In addition to polar (water-miscible) solvents such as nitrogen-containing organic solvents, such as cellosolve (registered trademark) such as methyl cellosolve, ethyl cellosolve, etc., such as toluene, xylene, benzene Carbonized water Halogenated hydrocarbon solvents such as elemental, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, esters such as methyl acetate and ethyl acetate Examples of the solvent include nitrogen-containing organic solvents such as nitromethane and nitroethane. These may be used alone or in combination of two or more.
Among them, polar (water-miscible) solvents such as tetrahydrofuran (THF) and halogenated hydrocarbons such as toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride, and ester systems such as ethyl acetate A combination with a non-water miscible solvent such as a solvent is particularly preferred.
The amount of the organic solvent used can be appropriately selected according to the purpose, but is preferably 200 to 200,000 parts by weight with respect to 1 part by weight of the precursor A- (B) m material. Further, the coating solution further contains a slight amount of a resin component that does not impair the achievement of the object of the present invention, a volatile or self-decomposable acid for promoting the decomposition of the carboester group, and a base material. Also good. Further, a strongly acidic solvent such as trichloroacetic acid (decomposed into chloroform and carbon dioxide by heating) and trifluoroacetic acid (volatile) is preferably used because it has an effect of expelling a carboester group which is a weak Lewis acid. And it can form by applying energy with respect to the film | membrane which consists of an organic-semiconductor precursor, and converting into an organic-semiconductor film.
These organic semiconductor thin film production methods include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, ink jet, dispensing, screen printing, and offset printing. Examples include printing methods such as printing, letterpress printing, flexographic printing, and soft lithography techniques such as microcontact printing, and a combination of a plurality of these techniques can be used. And according to material, a suitable solvent is selected from the said suitable film forming method and the said solvent.

In the organic thin film transistor of the present invention, the thickness of the organic semiconductor layer is not particularly limited, but a uniform thin film (that is, there is no gap or hole that adversely affects the carrier transport property of the organic semiconductor layer) is formed. The thickness is selected. The thickness of the organic semiconductor thin film is generally 1 μm or less, particularly preferably 5 to 200 nm.
In the organic thin film transistor of the present invention, the organic semiconductor layer formed using the above compound as a component is formed in contact with the source electrode, the drain electrode, and the insulating film.

“Filming method: Post-treatment of organic semiconductor film”
The characteristics of the organic semiconductor film converted from the precursor thin film can be improved by post-processing. For example, the heat treatment can alleviate distortion in the film generated during film formation, which leads to improvement in crystallinity, and can improve and stabilize characteristics. Further, by placing in an atmosphere of an organic solvent (for example, toluene, chloroform, etc.), it is possible to reduce distortion in the film and further enhance crystallinity as in the heat treatment.
Furthermore, a change in characteristics due to oxidation or reduction can be induced by exposure to an oxidizing or reducing gas or liquid such as oxygen or hydrogen. This can be used for the purpose of increasing or decreasing the carrier density in the film.

"electrode"
The gate electrode, source electrode, and gate electrode used in the organic thin film transistor of the present invention are not particularly limited as long as they are conductive materials, such as platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, lead, Tantalum, indium, aluminum, zinc, magnesium, etc., and their alloys and conductive metal oxides such as indium / tin oxide, or inorganic and organic semiconductors whose conductivity has been improved by doping, such as silicon single crystals, Examples thereof include polysilicon, amorphous silicon, germanium, graphite, polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline, polythienylene vinylene, polyparaphenylene vinylene, a complex of polyethylenedioxythiophene and polystyrene sulfonic acid.

The source electrode and the drain electrode are preferably those having low electrical resistance at the contact surface with the semiconductor layer among the above-described conductivity.
As a method for forming an electrode, a method of forming 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 above materials as a raw material, a metal such as aluminum or copper There is a method of etching using a resist by thermal transfer, ink jet or the like on a foil. Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from the coating film by lithography, laser ablation, or the like. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as a relief printing plate, an intaglio printing plate, a planographic printing plate or a screen printing method can also be used.
Moreover, the organic thin-film transistor of this invention can provide the extraction electrode from each electrode as needed.

"Insulating film"
Various insulating film materials can be used for the insulating film used in the organic thin film transistor of the present invention. For example, silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconium barium titanate, lead zirconate titanate, lead lanthanum titanate, titanate Examples thereof include inorganic insulating materials such as strontium, barium titanate, barium magnesium fluoride, bismuth tantalate niobate, and yttrium trioxide.

  Further, for example, polymer compounds such as polyimide, polyvinyl alcohol, polyvinylphenol, polyester, polyethylene, polyphenylene sulfide, unsubstituted or halogen atom-substituted polyparaxylylene, polyacrylonitrile, cyanoethyl pullulan, and the like can be used.

  Further, two or more of the above insulating materials may be used in combination. The material is not particularly limited, but a material having a high dielectric constant and a low electrical conductivity is preferable.

  Examples of the method for producing the insulating film layer using the above materials include a CVD method, a plasma CVD method, a plasma polymerization method, a dry process such as a vapor deposition method, a spray coating method, a spin coating method, a dip coating method, an ink jet method, and a cast method. Examples thereof include wet processes such as coating, blade coating, and bar coating.

"Organic semiconductor / insulating film interface modification such as HMDS"
In the organic thin film transistor of the present invention, an organic thin film may be provided between these layers for the purpose of improving the adhesion between the insulating film and the organic semiconductor layer, reducing the gate voltage, and reducing the leakage current. The organic thin film is not particularly limited as long as it does not chemically affect the organic semiconductor layer. For example, an organic molecular film or a polymer thin film can be used.

  Examples of the organic molecular film include a coupling agent using octyltrichlorosilane, octadecyltrichlorosilane, hexamethylenedisilazane, phenyltrichlorosilane and the like as specific examples. As the polymer thin film, the above-described polymer insulating film materials can be used, and these may function as a kind of insulating film. The organic thin film may be subjected to an anisotropic treatment by rubbing or the like.

"Protective layer"
The organic transistor of the present invention is stably driven even in the atmosphere, but a protective layer is used as necessary for protection from mechanical destruction, protection from moisture and gas, or protection for the convenience of device integration. Can also be provided.

"Applied devices"
The organic thin film transistor of the present invention can be used as an element for driving display image elements such as liquid crystal, organic EL, and electrophoresis, and by integrating them, a so-called “electronic paper” display can be manufactured. is there. Further, an IC in which the organic thin film transistor of the present invention is integrated can be used as a device such as an IC tag.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.
The identification of the compounds in the following examples is performed by NMR spectrum (JNM-ECX (trade name) 500 MHz, manufactured by JEOL Ltd.), mass spectrometry (GCMS-QP2010 Plus (trade name), manufactured by Shimadzu Corporation), elemental analysis (CHN) ( CHN recorder MT-2 (manufactured by Yanagimoto Seisakusho), elemental analysis (S) (ion chromatography → anion analysis system DX320 (trade name), manufactured by Dionex) was used. The purity of the compound was calculated from the peak area ratio using mass spectrometry (GCMS-QP2010 Plus (trade name), manufactured by Shimadzu Corporation) or LCMS (LCT Premire and Alliance (trade name), manufactured by Waters).

[Synthesis Example 1]
[Synthesis of specific compound intermediate 1]
<Synthesis of Compound 2>

Place 1, 2, 3, 4-tetrahydro-6-iodo naphthalene (10 g, 65.3 mmol of compound 1 in the above reaction formula) and 15% HCl (60 mL) in a 500 mL beaker and cool with ice 5 A sodium nitrite aqueous solution (5.41 g, 78.36 mmol in Water 23 mL) was gradually added dropwise while maintaining the temperature below ℃. After completion of the dropwise addition, the mixture was stirred for 1 hour at the same temperature, potassium iodide aqueous solution (13.0 g, 78.36 mmol in Water 50 mL) was added at once, the ice bath was removed and the mixture was stirred for 3 hours, and then nitrogen was generated at 60 ° C. Heated for 1 hour until fit. After cooling to room temperature, the reaction solution was extracted three times with diethyl ether. The organic layer was washed with 5% aqueous sodium thiosulfate solution (100 mL × 3 times), and further with saturated brine (100 mL × 2 times). Furthermore, it dried with sodium sulfate and the red oil was obtained by concentrating a filtrate.
This was purified by silica gel column chromatography (solvent: hexane) to obtain Compound 2 as a colorless oil. (Yield 12.0 g, Yield 71.2%)
The analysis results of Compound 2 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.73-1.81 (m, 4H), 2.70 (quint, 4H, J = 4.85 Hz), 6.80 (d, 1H, J = 8.0 Hz), 7.38 ( dd, 1H, J ₁ = 8.0 Hz J ₂ = 1.75 Hz), 7.41 (s, 1H)
Mass spectrometry: GC-MS m / z = 258 (M +)

<Synthesis of Compound 3>
The target compound was synthesized by applying the method described in J. Org. Chem. 1999, 64, 9365-9373.

Compound 2 (3.1 g, 12 mmol), azobisisobutyronitrile (59 mg, 0.36 mmol), carbon tetrachloride (50 mL), N-bromosuccinimide (4.7 g, 26.4 mmol) in a 100 mL round bottom flask After replacing with argon gas, the mixture was gently heated to 80 ° C., stirred for 1 hour as it was, and cooled to room temperature. The precipitate was filtered, and the filtrate was concentrated under reduced pressure to obtain Compound 3 as a pale yellow solid. (Yield 4.99 g, Yield 100%)
Used in the next reaction without further purification. The analysis results of Compound 3 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.31-2.41 (m, 2H), 2.70-2.79 (m, 2H), 5.65 (t
, 2H, J = 2.0 Hz), 7.24-7.28 (m, 2H), 7.31-7.34 (m, 2H) Mass spectrometry: GC-MS m / z = 413 (M +)

<Synthesis of Compound 4>
1,4-dibromo-1,2,3,4-tetrahydronaphthalene was used as a raw material in the same manner as Compound 3, synthesized by the method described in J. Org. Chem. 1999, 64, 9365-9373.

A 100 mL round bottom flask was charged with tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), acetic acid (1.21 g, 20 mmol), dimethylformamide (hereinafter DMF) (30 mL), and purged with argon. Stir at room temperature for 2.5 hours. 1,4-dibromo-1,2,3,4-tetrahydronaphthalene (2.90 g, 10 mmol) was added thereto, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a light brown solid. This was washed with hexane to obtain Compound 4 as a colorless solid. (Yield 1.50 g, Yield 60.6%, 5: 6 mixture of racemic and meso forms)
By recrystallization from hexane, the racemate and meso form were separated.
The analysis results of Compound 4 are shown below.
Racemic body
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.96-1.99 (m, 2H), 2.07 (s, 6H), 2.27-2.30 (m, 2H), 6.05 (t, 2H, J = 2.3 Hz ), 7.34 (br, 4H)
Meso body
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.09-2.12 (m, 4H), 2.13 (s, 6H), 5.96-5.98 (m, 2H), 7.32 (br, 4H)
Mass spectrometry: GC-MS m / z = 248 (M +)

<Synthesis of Compound 5>

Place tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), caproic acid (2.51 mL, 20 mmol), DMF (30 mL) in a 100 mL round bottom flask, purge with argon, and then at room temperature for 2.5 hours Stir. Compound 3 (4.16 g, 10 mmol) was added thereto, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give an orange oil. This was purified by silica gel column chromatography (solvent: toluene → ethyl acetate / toluene (5/95, v / v)) to obtain Compound 5 as a colorless oil. (Yield 2.44 g, Yield 50.2%) The analysis results of Compound 5 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.87-0.90 (m, 6H), 1.24-1.34 (m, 8H), 1.60-1.67 (m, 4H), 1.90-1.94 (m, 2H) , 2.23-2.34 (m, 6H), 5.98 (d, 2H, J = 3.5 Hz), 7.06 (d, 2H, J = 8.0 Hz), 7.63-7.66 (m, 2H)
Mass spectrometry: GC-MS m / z = 486 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 5.

<Synthesis of Compound 6>

Put tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), pivalic acid (2.04 g, 20 mmol), DMF (30 mL) in a 100 mL round bottom flask, purge with argon, and then 2.5 hours at room temperature Stir. Compound 3 (4.16 g, 10 mmol) was added thereto, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layers were washed with saturated sodium bicarbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a pale orange solid. This was recrystallized from ethanol (twice) to obtain Compound 6 as pale yellow crystals. (Yield 1.93 g, Yield 42.0%) The analysis results of Compound 6 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.18 (s, 18H), 1.20 (s, 18H), 1.87-1.92 (m, 4H), 2.21-2.24 (m, 4H), 5.94 (d , 4H, J = 2.3 Hz), 7.02 (d, 2H, J = 8.0 Hz), 7.62-7.63 (m, 2H), 7.64-7.65 (m, 2H)
Mass spectrometry: GC-MS m / z = 458 (M +)
Melting point: 114.0-115.5 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 6.

<Synthesis of Compound 7>

In a 100 mL round bottom flask, add tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), 3,3,3-trifluoropropanoic acid (2.56 g, 20 mmol), DMF (30 mL), argon After the replacement, the mixture was stirred at room temperature for 2.5 hours. Compound 3 (4.16 g, 10 mmol) was added thereto, and the mixture was further stirred at room temperature for 48 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layers were washed with saturated sodium bicarbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a brown liquid. This was purified by silica gel column chromatography (solvent: acetate / hexane (1/2, v / v) + 2% triethylamine added) to obtain a pale yellow oil. (Yield 2.44 g)
Furthermore, it refine | purified by recycle preparative HPLC (the Nippon Analytical Industrial Co., Ltd. make, LC-9104), and the compound 7 was obtained as colorless oil (yield 1.2 g, 25% of yield) Below, the analysis result of the compound 7 is shown. Show.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.99-2.31 (m, 4H, H2, H3), 3.14-3.30 (m, 4H, -CH2CF3), 5.96-6.08 (m, 2H, H1, H4), 7.05-7.10 (m, 1H, ArH), 7.66-7.71 (m, 2H, ArH)
Mass spectrometry: GC-MS m / z = 510 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 7.

[Synthesis Example 2]
[Synthesis of Compound Intermediate 2]
<Synthesis of Compound 8>

Thieno [3,2-b] thiophene (2.81 g, 20.0 mmol) was placed in a well-dried 200 mL round bottom flask, purged with argon, and dehydrated tetrahydrofuran (THF) (50 mL) was added. Then, it was cooled to -78 ° C in an acetone-dry ice bath, n-butyllithium (2.2 eq, 28.1 mL (1.6 M hexane solution), 44 mmol) was added dropwise over 15 minutes, and the reaction system was allowed to warm to room temperature. The mixture was warmed and stirred for 16 hours. The mixture was cooled again to −78 ° C., trimethyltin chloride (2.5 eq, 50 mL (1.0 M hexane solution), 50 mmol) was added all at once, the temperature of the reaction system was raised to room temperature, and the mixture was stirred for 24 hours.
Water (80 mL) was added to quench and ethyl acetate was added to separate the organic layer. The organic layer was washed with a saturated aqueous sodium carbonate solution and then with a saturated saline solution, further dried over sodium sulfate, and the filtrate was concentrated to obtain a brown solid. This was recrystallized from acetonitrile (repeated three times) to obtain Compound 8 as colorless crystals. (Yield 5.0 g, 54.1%)
The analysis results of Compound 8 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.38 (s, 18H), 7.23 (s, 2H)
Mass spectrometry: GC-MS m / z = 466 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 8.

<Synthesis of Compound 9>

Benzo [1,2-b: 4,5-b ′] dithiophene can be synthesized as described in J. Org. Chem., 2005, 70 (25), pp 10569-10571 and Org. Lett. What was synthesize | combined according to the method of 2009, 11 (11), pp 2473-2475 was used as a raw material.
Benzo [1,2-b: 4,5-b ′] dithiophene (3.81 g, 20.0 mmol) was placed in a well-dried 200 mL round-bottom flask, purged with argon, and dehydrated THF (50 mL), cooled to -78 ° C in an acetone-dry ice bath, and n-butyllithium (2.2 eq, 28.1 mL (1.6 M hexane solution), 44 mmol) was added dropwise over 15 minutes. The mixture was warmed to room temperature and stirred for 16 hours. The mixture was cooled again to −78 ° C., trimethyltin chloride (2.5 eq, 50 mL (1.0 M hexane solution), 50 mmol) was added all at once, the temperature of the reaction system was raised to room temperature, and the mixture was stirred for 24 hours. Water (80 mL) was added to quench and ethyl acetate was added to separate the organic layer. The organic layer was washed with a saturated aqueous sodium carbonate solution and then with a saturated saline solution, further dried over sodium sulfate, and the filtrate was concentrated to obtain a brown solid. This was recrystallized from acetonitrile (repeated three times) to obtain Compound 9 as pale yellow crystals. (Yield 7.48 g, 72.5%)
The analysis results of Compound 9 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.44 (s, 18H), 7.41 (s, 2H), 8.27 (s, 2H)
Mass spectrometry: GC-MS m / z = 518 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 9.

<Synthesis of Compound 10>

2,7-Diiodo [1] benzothieno [3,2-b] [1] benzothiophene is described in Zh. Org. Khim. 16, 2, 383 (1980) and J.A. Am. Chem. Soc. 128, 12604 (2006) was used as a raw material. 2, 7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.92 g, 10.0 mmol) was placed in a well-dried 300 mL round-bottomed flask and purged with argon. , Dehydrated THF (150 mL) was added, cooled to -78 ° C in an acetone-dry ice bath, and n-butyllithium (2.2 eq, 14.1 mL (1.6 M hexane solution), 22 mmol) was added dropwise over 15 minutes. The reaction system was warmed to room temperature and stirred for 16 hours. The mixture was cooled again to −78 ° C., trimethyltin chloride (2.5 eq, 25 mL (1.0 M hexane solution), 25 mmol) was added in one portion, the temperature of the reaction system was raised to room temperature, and the mixture was stirred for 24 hours. Water (80 mL) was added to quench, and chloroform was added to separate the organic layer. The organic layer was washed with a saturated aqueous sodium carbonate solution and then with a saturated saline solution, further dried over sodium sulfate, and the filtrate was concentrated to obtain a brown solid. This was recrystallized from toluene, followed by acetonitrile to obtain Compound 10 as light brown crystals. (Yield 3.40 g, 60.0%)
The analysis results of Compound 10 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.37 (s, 18H), 7.55 (d, 2H, J = 8.6 Hz), 7.87 (d, 2H, J = 7.5 Hz), 8.04 (s, 2H)
Mass spectrometry: GC-MS m / z = 566 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 10.
TTPTT-Sn
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.51 (s, 18H), 7.35 (s, 2H), 8.25 (d, 2H)

[Synthesis Example 3; Synthesis of precursor molecule]
<Synthesis of Compound 11>

Compound 5 (973 mg, 2.0 mmol), compound 8 (466 mg, 1 mmol) and DMF (10 mL) were placed in a 100 mL round bottom flask, and after bubbling with argon gas for 30 minutes, tris (dibenzylideneacetone) was added. ) Dipalladium (0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at room temperature for 20 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layer was washed with a saturated aqueous potassium fluoride solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a red liquid. This is purified by column chromatography (fixed layer: (neutral silica gel (Kanto Chemical) + 10 wt% potassium fluoride, solvent: hexane / ethyl acetate, 9/1 → 8/2, v / v) Gave a yellow solid which was recrystallized from hexane / ethanol to give compound 11 as a yellow solid (yield 680 mg, 79.3% yield).
)
The compound analysis results are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.87-0.89 (m, 12H), 1.28-1.33 (m, 16H), 1.61-1.69 (m, 8H), 1.96-2.01 (m, 4H) , 2.28-2.36 (m, 12H), 6.08 (d, 4H, J = 12.1 Hz), 7.37 (d, 2H, J = 8.6 Hz), 7.48 (s, 2H), 7.57-7.59 (m, 4H)
Melting point: 113.7-114.7 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 11.
Elemental analysis _{(C 50 H 64 O 8 S} 2): C, 69.92; H, 7.67; O, 14.85; S, 7.44 ( Found), C, 70.06; H, 7.53; O, 14.93; S, 7.48 ( theoretical value)

<Synthesis of Compound 12>

In a 100 mL round bottom flask, compound 6 (2.0 mmol, 917 mg), compound 8 (466 mg, 1 mmol) and DMF (10 mL) were placed, and after bubbling with argon gas for 30 minutes, tris (dibenzylideneacetone) was added. ) Dipalladium (0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at room temperature for 24 hours and then at 50 ° C. for 3 hours under an argon atmosphere. The reaction solution was diluted with toluene, insoluble materials were removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with toluene. The combined organic layers are washed with a saturated aqueous potassium fluoride solution followed by saturated brine, dried over magnesium sulfate, and the filtrate is concentrated. The resulting solid is washed with hexane to obtain compound 12 as a yellow solid. It was. (Yield 320 mg, Yield 40.0%)
The analysis results of Compound 12 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.21 (s, 18H), 1.24 (s, 18H), 1.90-1.96 (m, 4
H), 2.30 (dt, 4H, J ₁ = 9.2 Hz, J ₂ = 2.3 Hz), 6.03 (d, 4H, J = 13.2 Hz), 7.32 (d, 2
H, J = 8.0 Hz 7.46 (s, 2H), 7.53 (d, 2H, J = 1.7 Hz), 7.58 (dd, 2H, J ₁ = 8.0 Hz, J ₂
= 2.3 Hz)
Decomposition point: 275.2 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 12.
Elemental analysis _{(C 46 H 56 O 8 S} 2): C, 68.87; H, 6.95; O, 16.08; S, 8.10 ( Found), C, 68.97;
H, 7.05; O, 15.98; S, 8.01 (theoretical value)

<Synthesis of Compound 13>

Compound 100 (1020 mg, 2.0 mmol), compound 8 (466 mg, 1 mmol), DMF (10 mL) were placed in a 100 mL round bottom flask, and argon gas was bubbled for 30 minutes, followed by tris (dibenzylideneacetone). ) Dipalladium (0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at room temperature for 16 hours and then at 80 ° C. for 8 hours under an argon atmosphere. The reaction solution was diluted with ethyl acetate, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. This was purified by column chromatography (fixed layer: (neutral silica gel (Kanto Chemical) + 10 wt% potassium fluoride, solvent: hexane / ethyl acetate (2/1, v / v) + 2% triethylamine added)) As a result, a yellow solid was obtained.
Furthermore, it refine | purified by recycle preparative HPLC (the Japan Analytical Industrial Co., Ltd. LC-9104, solvent: THF), and the compound 13 was obtained as a pale yellow crystal | crystallization (yield 200 mg, yield 22.1%)
The analysis results of Compound 13 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.06-2.35 (m, 8H, H2, H3 of Tetralin), 3.16-3.3.33 (m, 8H, -CH2CF3), 6.07-6.18 (m, 4H, H1, H4 of Tetralin), 7.36-7.41 (m, 2H, ArH), 7.50 (d, 2H, J = 6.9 Hz, ArH), 7.57-7.64 (m, 4H, ArH)
Decomposition point: 197.5 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 13.
Elemental analysis (C ₃₈ H ₂₈ F ₁₂ O ₈ S ₂ ): C, 50.65; H, 3.02; O, 14.00; S, 7.19 (actual value), C, 50.45; H, 3.12; O, 14.15; S, 7.09 (Theoretical value)

<Synthesis of Compound 14>

In a 100 mL round bottom flask, compound 7 (1887 mg, 3.7 mmol), compound 9 (929 mg, 1.8 mmol) and DMF (25 mL) were placed, and after bubbling with argon gas for 30 minutes, tris (dibenzylideneacetone) was added. ) Dipalladium (0) (32.9 mg, 0.036 mmol) and tri (orthotolyl) phosphine (43.9 mg, 0.144 mmol) were added, and the mixture was stirred at 80 ° C. for 4 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. This was purified by recycle preparative HPLC (manufactured by Nippon Analytical Industrial Co., Ltd., LC-9104, solvent: THF) to obtain Compound 14 as light yellow crystals (yield 340 mg, yield 20.0%).
The analysis results of Compound 14 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.08-2.37 (m, 8H, H2, H3 of Tetralin), 3.20-3.3.34 (m, 8H, -CH2CF3), 6.09-6.6.21 ( m, 4H, H1, H4 of Tetralin), 7.40-7.47 (m, 2H, ArH), 7.60 (d, 2H, J = 7.5 Hz, ArH), 7.68-7.75 (m, 4H, ArH), 8.22 (s , 2H)
Decomposition point: 231 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 14.
Elemental analysis _{(C 42 H 30 F 12 O} 8 S 2): C, 52.74; H, 3.28; O, 13.70; S, 6.52 ( Found), C, 52.
83; H, 3.17; O, 13.41; S, 6.72 (theoretical value)

<Synthesis of Compound 15>

In a 100 mL round bottom flask, compound 5 (1020 mg, 2.1 mmol), compound 10 (492 mg, 1.0 mmol), DMF / toluene (25 mL) were added, and argon gas was bubbled for 30 minutes. Benzylideneacetone) dipalladium (0) (32.9 mg, 0.036 mmol) and tri (orthotolyl) phosphine (43.9 mg, 0.144 mmol) were added, and the mixture was stirred at 80 ° C. for 12 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. This was purified by column chromatography (fixed layer: (neutral silica gel (Kanto Chemical) + 10 wt% potassium fluoride, solvent: dichloromethane / ethyl acetate (3/1, v / v) + 2% triethylamine added)) As a result, a yellow solid was obtained.
Subsequently, it was purified by recycle preparative HPLC (manufactured by Nihon Analytical Industrial Co., Ltd., LC-9104, solvent: THF) to obtain Compound 15 as pale yellow crystals (yield 210 mg, yield 42.7%).
The analysis results of Compound 15 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.85-0.91 (m, 12H), 1.29-1.33 (m, 16H), 1.63-
1.69 (m, 8H), 1.99-2.04 (m, 4H), 2.32-2.37 (m, 12H), 6.15 (d, 4H, J = 18.9 Hz), 7
.46 (d, 2H, J = 8.0 Hz), 7.65-7.69 (m, 6H), 7.95 (d, 2H, J = 8.0 Hz), 8.11 (d, 2H,
(J = 1.2 Hz)
Melting point: 179.0 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 15.
Elemental analysis _{(C 58 H 68 O 8 S} 2): C, 72.50; H, 7.43; O, 13.57; S, 6.49 ( Found), C, 72.77
; H, 7.16; O, 13.37; S, 6.70 (theoretical value)

<Synthesis of Compound 16>

In a 100 mL round bottom flask, compound 7 (1020 mg, 2.1 mmol), compound 10 (492 mg, 1.0 mmol), DMF / toluene (25 mL) were charged, and argon gas was bubbled for 30 minutes. Benzylideneacetone) dipalladium (0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at 80 ° C. for 8 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. This was purified by column chromatography (fixed layer: (neutral silica gel (Kanto Chemical) + 10 wt% potassium fluoride, solvent: dichloromethane / ethyl acetate (3/1, v / v) + 2% triethylamine added)) As a result, a yellow solid was obtained.
Subsequently, purification was performed by recycle preparative HPLC (manufactured by Nippon Analytical Industries, Ltd., LC-9104, solvent: THF) to obtain Compound 16 as light yellow crystals (yield 180 mg, yield 36.5%).
The analysis results of Compound 16 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.08-2.38 (m, 8H, H2, H3 of Tetralin), 3.19-3
.33 (m, 8H, -CH2CF3), 6.12-6.25 (m, 4H, H1, H4 of Tetralin), 7.48-7.50 (m, 2H, Ar
H), 7.65-7.73 (m, 6H, ArH), 7.97 (d, 2H, J = 8.6 Hz, ArH), 8.12 (d, 2H, J = 1.2 Hz,
ArH)
Decomposition point: 218 ℃
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 16.
Elemental analysis (C ₄₆ H ₃₂ F ₁₂ O ₈ S ₂ ): C, 55.17; H, 3.41; O, 12.95; S, 6.07 (theoretical), C, 54.98; H, 3.21; O, 12.74; S, 6.38 (Theoretical value)

[Example of thin film production]
Hereinafter, examples of the method for producing a film-like body of the present invention will be described in some detail first, and then, as a concise disclosure for facilitating understanding of the technical essential parts of the present invention, the core precursor A The details of the conversion to the target compound A- (C) m by elimination of the leaving group from-(B) m will be explained in detail by specific examples, and together with the precursor A- (B) m Although the solubility in an organic solvent will also be described in detail, the conversion to the target compound A- (C) m by elimination of the leaving group from the precursor A- (B) m is not reversible. It is believed that it is not difficult to understand that it directly indicates the production method of the target compound A- (C) m by elimination of the leaving group from the isomer A- (B) m.

Compound 11, Compound 14, and Compound 15 (5 mg each) synthesized in Synthesis Example 3 were dissolved in THF to a concentration of 0.1 wt%, and filtered through a 0.2 μm filter to prepare a solution. . 100 μL of the prepared solution is dropped on an N-type silicon substrate having a thermal oxide film having a thickness of 300 nm that has been washed in concentrated sulfuric acid for 24 hours, placed on a petri dish, and left to stand until the solvent is dried. A thin film was prepared. When this thin film was subjected to a polarizing microscope and a scanning probe microscope (contact mode, Nanopics (trade name), manufactured by Seiko Instruments Inc.), it was found that a smooth continuous amorphous film was obtained. Next, the thin film was annealed at 250 ° C. for 30 minutes in an argon atmosphere, and the film was observed in the same manner as described above. After the annealing treatment, a plurality of colored domains were observed with a polarization microscope, and it was found that a smooth crystalline film was obtained. This is because compound 11, compound 14, and compound 15 which are precursors eliminate the ester group which is a soluble group, so that compound 17, compound 18, and compound 19 having stronger intermolecular interaction in the film. This is because it has been converted into crystalline.
This thin film was insoluble in chloroform, THF, toluene and the like at 25 ° C.

[Example of leaving behavior of leaving group of compound 11]
The compound 11 (5 mg) synthesized in Synthesis Example 3 was placed on a hot plate set at an arbitrary temperature (150, 160, 170, 180, 220, 230, 240, 260 ° C.) through a silicon wafer for 30 minutes. The sample was prepared by heating.
IR spectra (KBr method, Spectrum GX (trade name), manufactured by Perkin Elmer) of the sample, the compound precursor 11 before heating, and the compound 17 after conversion were measured. The result is shown in FIG.
Under the heating condition of Compound 11 at 240 ° C., the absorption of —O— (1156 cm ⁻¹ and C═O (1726 cm ⁻¹⁾ ) disappears, and new absorption (810, 738, 478 cm ⁻¹⁾ The existence of the tribe was confirmed. This is consistent with the spectrum of compound 17.
Further, the thermal decomposition behavior of Compound 11 was measured at 25 ° C. to 500 ° C. using TG-DTA (reference Al ₂ O ₃ , under a nitrogen stream (200 mL / min), EXSTAR6000 (trade name), manufactured by Seiko Instruments Inc.). The temperature was increased at a rate of 5 ° C./min and observed. The result is shown in FIG.
In TG-DTA, a weight loss of 56.7% was observed from 160 to 290 ° C. This is almost consistent with 4 molecules of caproic acid (theoretical value: 54.2%). The presence of a melting point was observed at 357.7 ° C. This is consistent with the value of compound 17.
From the above results, it was shown that compound 11 was converted to compound 17 by heating.
It was also shown that the desorption reaction threshold was around 240 ° C.

[Example of leaving group leaving group of compound 12]
A sample was prepared in the same manner except that the compound 11 of Example 2 was replaced with the compound 12 and the heating conditions were 170, 180, 200, 220, 240, 250, 260, 280, 300 ° C., and the IR spectrum was measured. The conversion temperature was estimated.
Under the heating condition of Compound 12 at 280 ° C., absorption of —O— (1156 cm ⁻¹ and C═O (1726 m ⁻¹⁾ ) disappears, and new absorption (810, 738, 478 cm ⁻¹⁾ The existence of the tribe was confirmed. Similarly, TG-DTA was measured. In TG-DTA, a weight loss of 58.2% was observed from 250 to 285 ° C. This is somewhat larger than 4 molecules of pivalic acid (theoretical 51.0%). The presence of a melting point was observed at 357.2 ° C. This is consistent with the value of compound 17.
From the above results, it was shown that Compound 12 was converted to Compound 17 by heating.
It was also shown that the threshold for elimination reaction was around 280 ° C.

[Example of elimination behavior of leaving group of compound 15]
A sample was prepared in the same manner except that the compound 11 of Example 2 was replaced with the compound 15 and the heating conditions were 180, 200, 220, 230, 240, 250, 260, 280 ° C., the IR spectrum was measured, and the IR spectrum was measured. The conversion temperature was measured and estimated. Under the heating condition of Compound 15 at 25 ° C., the absorption of —O— (1156 cm ⁻¹ and C═O (1726 cm ⁻¹⁾ ) disappears, and new absorption (810, 738, 478 cm ⁻¹⁾ , aromatic ) Was confirmed. This is consistent with the spectrum of compound 19. Similarly, TG-DTA was measured. In TG-DTA, a weight loss of 50.7% was observed from 200 to 300 ° C. This is almost consistent with 4 molecules of caproic acid (theoretical value 48.5%). The presence of a melting point was observed at 358.2 ° C. This is consistent with the value of compound 19. From the above results, it was shown that Compound 15 was converted to Compound 19 by heating.
It was also shown that the threshold for elimination reaction is around 250 ° C.
From the above examples, the desorption behavior and the threshold temperature of the desorption reaction could be estimated. In addition, the effect of the combined π-electron conjugated core was not so great, and it was shown that the temperature at which the elimination reaction occurs was changed by the difference in the alkyl chain introduced into the ester moiety. The higher the acidity of the alkyl chain, that is, the carboxylic acid as the elimination component (which can be expressed in pKa), the lower the elimination temperature. Each pKa is pivalic acid (5.0), caproic acid (4.6), 3,3,3-trifluoropropionic acid (3.0).
In the case of the compound in the present invention, it was shown that the target π-electron conjugated compound can be obtained by heating to approximately 250 ° C.
In Examples 2 to 4, the actual weight loss is larger than the theoretical value because the sublimation properties of Compound 17 and Compound 19 are relatively high because of high temperature and under a nitrogen stream. This is probably because the body crystals contain a solvent.

[Solubility example]
Compounds 11 to 19 synthesized in Synthesis Example 3 were respectively added to toluene, THF, anisole and chloroform (2.0 mg each) until they remained undissolved, stirred for 10 minutes under reflux of the solvent, cooled to room temperature and further cooled. After stirring for 1 hour and allowing to stand for 16 hours, the supernatant was filtered through a 0.2 μm PTFE filter to obtain a saturated solution. This was dried under reduced pressure to calculate the solubility of the precursor in each solvent. The results are shown in Table 5.
(In Table 4, ◎ means a solubility of 0.5 wt% or more, ○ means 0.1 wt% or more and less than 0.5 wt%, Δ means 0.005 wt% or more and less than 0.1 wt%, X indicates that it was less than 0.005 wt%.)
From this, it was found that the solvent has a solubility of about 0.1 wt% or more in a large number of solvents having different polarities, and it is clear that the selectivity of the solvent in the coating process is rich. Moreover, compound 17, compound 18, and compound 19, which are the materials after conversion, are soluble in 0.005 wt% or less in all these solvents, suggesting that the converted compounds are insolubilized by the elimination reaction. .

 [Example 1 of conversion to target compound A- (C) m by elimination of leaving group; Synthesis example 5 of compound having benzene ring (synthesis of naphthalene)]

Compound 4 (100 mg) synthesized in Synthesis Example 1 was placed in a round bottom flask and stirred for 1 hour while maintaining the internal temperature at 180 ° C. Subsequently, a glass tube equipped with a cooling part with ice was placed on the flask, the inside of the flask was depressurized (40 mmHg), and sublimation purification was carried out by continuing heating at an internal temperature of 80 ° C. Crystals were scraped off (Yield 51.5 mg, Yield 99.8%)
The following analysis of this crystal was performed.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 7.48 (d, 4H, J ₁ = 6.8 Hz), 7.84 (d, 4H, J ₁ = 8.3 Hz)
Elemental analysis: C, 93.46; H, 6.44 (actual value) C, 93.71; H, 6.29 (theoretical value)
Mass spectrometry: GC-MS m / z = 128 (M +)
Melting point: 79.0-80.0 ° C was obtained.
Compound purity (LC-MS): ≥99.9%
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were naphthalene.

[Synthesis Example 6 of a Compound Having a Benzene Ring (Synthesis of 2-iodonaphthalene 1)]

Compound 5 (97.28 mg, 0.2 mmol) synthesized in Synthesis Example 1 was placed in a round bottom flask and stirred for 1 hour with an internal temperature of 180 ° C. Subsequently, a glass tube equipped with an ice cooling part was placed on the flask, the inside of the flask was depressurized (40 mmHg), and sublimation purification was carried out by continuing heating at an internal temperature of 50 ° C. Crystals were scraped off (yield 50.66 mg, yield 99.7%)
When the following analysis of this crystal was performed,
¹ H NMR (400 MHz, CDCl ₃ , TMS, δ): 7.46-7.52 (m, 2H) 7.55-7.58 (m, 1H), 7.68-7.74 (m, 2H), 7.76-7.82 (m, 1H), 8.22-8.26 (m, 1H)
Elemental analysis (C10H7I): C, 47.11; H, 2.94 (actual measurement) C, 47.27; H, 2.78 (theoretical)
Mass spectrometry: GC-MS m / z = 254 (M +)
Melting point: 50.5-52.0 ° C was obtained.
Compound purity (LC-MS): ≧ 99.8%
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were 2-iodonaphthalene.

[Synthesis Example 7 of Compound Having Benzene Ring (Synthesis 2 of 2-iodonaphthalene 2)]
The reaction was performed in the same manner except that the compound 5 used in Example 7 was changed to the compound 6 (91.67 mg, 0.2 mmol).
Colorless crystals adhering to the glass tube were scraped off (yield 50.46 mg, yield 99.3%).
When the following analysis of this crystal was performed, the same analysis results as in Example 7 were obtained.
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were 2-iodonaphthalene.

[Synthesis of compounds having a benzene ring 8 (Synthesis of 2-iodonaphthalene 3)]
The reaction was performed in the same manner except that the compound 6 used in Example 8 was replaced with the compound 7 (102.0 mg, 0.2 mmol) and the internal temperature of the flask was changed to 160 ° C.
Colorless crystals adhering to the glass tube were scraped off (yield 50.76 mg, yield 99.9%).
When the following analysis of this crystal was performed, the same analysis results as in Example 7 were obtained.
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were 2-iodonaphthalene.
From Examples 5 to 8, it was shown that naphthalene and derivatives thereof were obtained at a relatively low temperature of 180 ° C. or less and a high yield of 99% or more. It was also shown that the reaction was completed at a lower temperature in a compound having an alkyl group with high electron-withdrawing properties such as partially halogenated (fluorinated).

[Synthesis Example 1 of Compound 17]

Compound 11 (200 mg, 0.23 mmol) synthesized in Synthesis Example 3 was placed in a round bottom flask, and heated and stirred at 245 ° C. (inner temperature of the flask) for 1 hour under an argon atmosphere.
The obtained solid was washed with toluene, followed by methanol, and dried under vacuum to obtain Compound 17 as yellow crystals. (Yield 86.9 mg, Yield 96.3%)
The analysis results of Compound 17 are shown below.
Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.84; H, 4.00; S, 16.10 (actual measurement) C, 79.55; H, 4.11; S, 16.34 (theoretical value) Mass spectrometry: GC-MS m / z = 392 (M +)
Melting point: 357.7 ° C
Compound purity (GCMS): ≥99.8%

From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 17.

[Synthesis 2 of Compound 17]

The reaction and purification were carried out in the same manner as in Example 10 except that the compound 11 used in Example 10 was replaced with the compound 12 (184.2 mg, 0.23 mmol) and the reaction temperature was changed to 270 ° C.
Similarly, Compound 17 was obtained as yellow crystals. (Yield 86.3 mg, Yield 96.3%)
The analysis results of Compound 17 obtained by this reaction are shown below.
Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.64; H, 4.10; S, 16.20 (actual value) C, 79.55; H, 4.11; S, 16.34 (theoretical value) Mass spectrometry: GC-MS m / z = 392 (M +)
Melting point: 357.2 ° C
Compound purity (GCMS): ≥99.7%

From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 17.

[Synthesis 3 of Compound 17]

The reaction and purification were carried out in the same manner as in Example 10 except that the compound 11 used in Example 10 was changed to the compound 13 (219.6 mg, 0.23 mmol) and the reaction temperature was changed to 200 ° C.
Similarly, Compound 17 was obtained as yellow crystals. (Yield 89.2 mg, Yield 98.8%)
The analysis results of Compound 17 obtained by this reaction are shown below.
Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.58; H, 4.11; S, 16.32 (actual value) C, 79.55; H, 4.11; S, 16.34 (theoretical value) Mass spectrometry: GC-MS m / z = 392 (M +)
Melting point: 357.2 ° C
Compound purity (GCMS): ≥99.7%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 17.

[Synthesis of Compound 18]

The reaction was conducted in the same manner as in Example 10 except that the compound 11 used in Example 10 was replaced with the compound 14 (208.1 mg, 0.23 mmol) and the reaction temperature was changed to 240 ° C. The resulting solid was treated with chloroform, acetone, The compound 18 was obtained as yellowish green crystals by washing with methanol and drying under vacuum. (Yield 100 mg, Yield 98.3%)
The analysis results of Compound 18 obtained by this reaction are shown below.
Elemental analysis (C ₃₀ H ₁₈ S ₂ ): C, 81.21; H, 4.10; S, 14.59 (actual measurement) C, 81.41; H, 4.10; S, 14.49 (theoretical value) Mass spectrometry: GC-MS m / z = 442 (M +)
Melting point: 438.2 ° C
Compound purity (GCMS): ≥99.8%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 18.

[Synthesis 1 of Compound 19]

Compound 11 used in Example 10 was replaced with Compound 15 (208.1 mg, 0.23 mmol), and the reaction was carried out in the same manner as in Example 10 except that the reaction temperature was changed to 255 ° C., washed with chloroform and methanol, and then under vacuum. By drying, compound 19 was obtained as pale yellow crystals. (Yield 110 mg, Yield 97.1%)
The analysis results of Compound 19 obtained by this reaction are shown below.
Elemental analysis (C ₃₄ H ₂₀ S ₂ ): C, 82.67; H, 4.10; S, 13.14 (actual measurement) C, 82.89; H, 4.09; S, 13.02 (theoretical value) Mass spectrometry: GC-MS m / z = 492 (M +)
Melting point: 378.2 ° C
Compound purity (GCMS): ≧ 99.5%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 19.

[Synthesis 2 of Compound 19]

Compound 11 used in Example 10 was converted to Compound 16 (208.1 mg, 0.23 mmol)
Instead, the reaction was carried out in the same manner as in Example 10 except that the reaction temperature was changed to 220 ° C., washed with chloroform, acetone and methanol, and dried under vacuum to obtain Compound 19 as pale yellow crystals. (Yield 111.8 mg, Yield 98.7%)
The analysis results of Compound 19 obtained by this reaction are shown below.
Elemental analysis (C ₃₄ H ₂₀ S ₂ ): C, 82.52; H, 4.08; S, 13.17 (actual measurement) C, 82.89; H, 4.09; S, 13.02 (Theoretical value) Mass spectrometry: GC-MS m / z = 492 (M +)
Melting point: 377.9 ° C
Compound purity (GCMS): ≥99.4%

From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 19.
From the results of Examples 10 to 15, it was confirmed that a slightly soluble π-electron conjugated compound with a high yield of 97% or more and a high purity of 99% or more was obtained only by heating and washing operations at about 200-250 ° C. It was shown that it is possible to obtain. It was also found that the temperature required for the conversion was approximately below the sublimation temperature of each compound (defined as 1% weight loss temperature). For example, after the end of weight loss that occurs during conversion in Fig. 2, the graph shows an almost horizontal region from 300 ° C to 340 ° C, and since the weight loss starts at 1% or higher at higher temperatures, the compound sublimates. I can think of you.
This suggests that this is an effective method not only for the production of π-electron conjugated compounds which are not only soluble in organic solvents such as naphthalene but also are hardly soluble in organic solvents. It can also be applied to pigments, organic semiconductor molecules, and many other molecules.

[Comparative Example 1]
As Comparative Example 1, the solution of the solution was changed in the same manner except that Compound 11, Compound 14, and Compound 15 of Example 15 were changed to Compound 17, Compound 18, and Compound 19 and dichlorobenzene heated to 150 ° C. was used instead of THF. Adjustment and preparation of a thin film were performed.
In any of the films, crystals were deposited to the extent that they were visually confirmed, and it was confirmed that the films were discontinuous. Even in the polarization microscope, a plurality of discontinuous and colored domains were observed. When confirmed with a scanning probe microscope, a surface roughness of 100 μm or more was observed.
From the above results, it was shown that the production method of the present invention is effective in thinning a poorly soluble compound that only slightly dissolves in some high-boiling solvents.

  Although the application example of the manufacturing method of the (pi) conjugated compound of this invention is described below, an application example is not restricted to these.

[Application Example 1]
[Fabrication and evaluation of field effect transistors by solution process]
In the same manner as in Example 1, thin films containing the compound 11 were prepared on the substrates cleaned by the same method as in Example 1. The thin film was subjected to an annealing treatment at 250 ° C. for 30 minutes in an argon atmosphere to convert the thin film into a thin film (thickness: 50 nm) comprising Compound 17.
By using a shadow mask on top of this thin film, gold is vacuum-deposited (back pressure ^{-10 -4} Pa, deposition rate 1-2 Å / s, film thickness: 50 nm) to form source and drain electrodes (channel length 33 μm, A channel width 2 mm) was formed, and a field effect transistor (FET) element having the structure of FIG. The organic semiconductor layer and the silicon oxide film at portions different from the gold electrode were scraped off, and a conductive paste (conductive paste, manufactured by Fujikura Kasei) was applied to the portion, and the solvent was dried.
Using this portion, a voltage was applied to the silicon substrate as the gate electrode.
As a result of evaluating the electrical characteristics of the FET element thus obtained using a semiconductor parameter analyzer B1500A manufactured by Agilent (measurement conditions: source drain voltage fixed at −100 V, gate voltage swept from −20 V to +100 V), p-type The characteristic as a transistor element was shown. The field effect mobility was obtained from the saturation region in the current-voltage (IV) characteristics of the organic thin film transistor.
In addition, the following calculation formula (1) was used for calculation of the field effect mobility of an organic thin-film transistor.
Ids = μCinW (Vg−Vth) 2 / 2L Formula (1)
(Where Cin is the capacitance per unit area of the gate insulating film, W is the channel width, L is the channel length, Vg is the gate voltage, Ids is the source / drain current, μ is the mobility, and Vth is the gate that the channel begins to form. (It is the threshold voltage.)
Further, the ratio of the on-current at 0 V to the on-current at the gate voltage of 100 V was calculated as the on-off ratio.
As a result, a saturation mobility of 4.8 × 10 ⁻³ cm ² / Vs and an on / off ratio of 3 × 10 ⁵ were obtained.

[Application Example 2]
An organic transistor was prepared and evaluated in the same manner except that Compound 11 was replaced with Compound 14 in Application Example 1.
As a result, a saturation mobility of 2.7 × 10 ⁻³ cm ² / Vs and an on / off ratio of 3 × 10 ⁵ were obtained.

[Application Example 3]
An organic transistor was prepared and evaluated in the same manner except that Compound 11 was replaced with Compound 15 in Application Example 1.
As a result, a saturation mobility of 2.7 × 10 ⁻² cm ² / Vs and an on / off ratio of 3 × 10 ⁶ were obtained.
From the above application examples, it is clear that all the field effect transistors produced by using the production method of the present invention have good hole mobility and current on / off ratio, and have excellent characteristics as organic transistors. became. From this, it was shown that the production method of the present invention is useful also in the production of organic electronic device elements such as organic transistors.

According to the production method of the present invention, a π-electron conjugated compound containing a benzene ring without generating a terminal olefin by utilizing an elimination reaction by applying energy from a precursor excellent in solubility in various organic solvents Can be synthesized in a high yield, so that the process ability is excellent.
In the film formation of a compound that can be obtained only by vacuum film formation because it is hardly soluble, the continuous film can be easily obtained even by using a wet process by using the production method of the present invention. The method can be applied to organic electronic devices, especially electronic devices such as semiconductors, optical-electronic devices such as EL light-emitting devices, photoelectric conversion devices such as thin-film solar cells and dye-sensitized solar cells, electronic paper, various sensors, It may be applicable to RFIDs (radio frequency identification).

1 Organic Semiconductor Layer 2 Source Electrode 3 Drain Electrode 4 Gate Electrode 5 Gate Insulating Film

Japanese Patent Laid-Open No. 5-05568 WO2006-077788 JP-A-7-188234, JP 2008-226959 A JP 2007-224019 A JP 2008-270843 A JP 2009-105336 A JP 2009-84555 A JP 2006-352143 A

Appl. Phys. Lett. 72, p1854 (1998) J. et al. Am. Chem. Soc. 128, p12604 (2006) Nature, .388, p131, (1997) Adv. Mater. , 11, p480 (1999), J. et al. Appl. Phys. 100, p034502 (2006) Appl. Phys. Lett. 84, 12, p2085 (2004) J. et al. Am. Chem. Soc. 126, p1596 (2004)

Claims (6)

Desorption represented by the following general formulas (IIa) and (IIb) from a coating film formed by applying a coating solution of a solvent containing a π-electron conjugated compound precursor A- (B) m to a substrate. A method for producing a film-like body comprising producing a film-like body containing a π-electron conjugated compound represented by A- (C) m by removing a functional substituent.

(Here, A is a π-electron conjugated substituent, B is a solvent-soluble substituent having at least a partial structure of the structure represented by the above general formula (I), m is a natural number. , B is linked to any atom on A except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) in the above general formula (I) via a covalent bond , A is condensed with any carbon atom except the carbon atom at the substitution position of (X ₁ , X ₂ ), (Y ₁ , Y ₂ ) on A. C is represented by the above general formula (II) It has a structure as at least a partial structure.
In the general formulas (I) and (II), (X ₁ , X ₂ ) are both substituted or unsubstituted acyloxy groups having 1 or more carbon atoms, and (Y ₁ , Y ₂ ) are both hydrogen atoms. is there. R _{1 to} R ₄ are hydrogen atoms.   The method for producing a film-like body according to claim 1, wherein the coating liquid is applied by a method selected from the group consisting of inkjet coating, spin coating, solution casting, and dip coating. .   The substituent A includes (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound in which two or more rings are condensed, and (ii) the rings of (i) 3. The method for producing a film-like body according to claim 1, wherein at least one π-electron conjugated compound is selected from the group consisting of compounds linked by a covalent bond. The film-like body according to any one of claims 1 to 3, wherein the components (X ₁ -Y ₁ and X ₂ -Y ₂ ) desorbed from the compound A- (B) m are carboxylic acids. Manufacturing method.



The compound A- (B) m is solvent-soluble, the compound A- (C) m produced by elimination of the leaving substituent is solvent-insoluble, and the solvent is toluene, tetrahydrofuran, anisole or chloroform The method for producing a film-like body according to any one of claims 2 to 4, wherein: The method for producing a film-like body according to any one of claims 1 to 5, wherein the substituents B and C have partial structures represented by the following general formulas (III) and (IV).

_{(Wherein, X 1, X 2, Y} 1, Y 2 and _R 1 to R ₄ is to Table Wa substituents of the meaning)

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