JP2012216669A - METHOD OF FORMING FILM-LIKE BODY CONTAINING π ELECTRON CONJUGATED COMPOUND HAVING AROMATIC RING, AND METHOD OF PRODUCING π ELECTRON CONJUGATED COMPOUND - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of obtaining a π electron conjugated compound by imparting low energy, and an efficient method of forming a continuous film of a slightly-soluble π electron conjugated compound utilizing that technology, and to apply the thin film to an organic electronic device.SOLUTION: In the production method of a film-like body, a film-like body obtaining a π electron conjugated compound represented by (Ia) is produced by desorbing a desorption substituent represented by formula (II) by means of a coating film formed by coating a substrate with a coating liquid of solvent containing a π electron conjugated compound precursor (I). (In the formulae (I), (Ia), (II), X and Y represent a hydrogen atom or a desorption substituent. Q-Qare a hydrogen atom, a halogen atom, or a univalent organic group, independently, Qand Qare a hydrogen atom, a halogen atom, or a univalent organic group other than the desorption substituent. Q-Qmay form a ring by bonding the adjoining groups).

Description

  The present invention provides a specific substituent from a π-electron conjugated compound precursor containing a cyclohexadiene ring that is easy to synthesize and has a high solubility in organic solvents, and can be thermally converted by applying energy at a lower temperature than in the past. The present invention relates to a method for producing a film-like body containing a π-electron conjugated compound containing an aromatic ring (for example, a benzene ring), and a method for producing the compound in a simple and high yield. It is useful in the manufacture of organic electroluminescence (EL) and organic electronic devices such as organic semiconductors and organic solar cells, and is also useful in the production of organic pigments and organic dyes.

  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, WO 2006-077788 of Patent Document 2, and Appl. Phys. Lett. 72, p 1854 (1998) of Non-Patent Document 1, Non-Patent Document 2 J. Am. Chem. Soc. 128, p12604 (2006)), organic dyes, organic pigments, and the like. 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 (see, 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, Japanese Patent Application Laid-Open No. 2009-188386 in Japanese Patent Application Laid-Open No. JP-A-2009-239293 of Patent Document 9, JP-A 2009-28394 of Patent Document 10, Adv. Mater., 11, p480 (1999) of Non-Patent Document 4, and J. Appl of Non-Patent Document 5. Phys.100, p034502 (2006), Appl.Phys.Lett.84, 12, p2085 (2004) of Non-Patent Document 6, and J.Am.Chem.Soc.126, p1596 (2004) of Non-Patent Document 7. ).
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, a method has been proposed in which a precursor having a sulfonate ester-based substituent group is externally stimulated to eliminate the substituent group and replace it with a hydrogen atom to convert it into phthalocyanine. (For example, Japanese Patent Application Laid-Open No. 2009-84555 of Patent Document 11 and Japanese Patent Application Laid-Open No. 2009-88483 of Patent Document 12).
However, this method has a problem that the sulfonic acid ester has a high polarity, so that the solubility in a nonpolar organic solvent is not sufficient, and the temperature required for the conversion from the precursor is relatively high at 250 to 300 ° C. It was.

  In addition, olefinic oligothiophene and olefin substituted [1] benzothieno [3] are obtained by solubilizing by introducing a carboxylate having an alkyl chain at the molecular terminal β-position of oligothiophene and removing it by applying heat. , 2-b] [1] benzothiophene has been proposed (for example, Japanese Patent Application Laid-Open No. 2006-352143 in Patent Document 13, Japanese Patent Application Laid-Open No. 2009-275032 in Patent Document 14, Non-Patent Document 7). J. Am. Chem. Soc. 126, p 1596 (2004)). 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 molecular end after conversion, and this 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 above-mentioned conventional compounds have problems in the solubility of the precursor, the safety of the elimination component, the conversion temperature, and the stability of the compound after the conversion, and it is difficult to obtain a desired intermediate in the synthesis.
In order to solve the above problems, the present inventors have proposed a π-electron conjugated compound precursor (precursor) based on a cyclohexene skeleton having an acyloxy group (specifically, a carboxylic acid ester) structure as a leaving group. Then, the structure after elimination is not an olefin group as described above (olefin-substituted oligothiophene or olefin-substituted [1] benzothieno [3,2-b] [1] benzothiophene) but a benzene ring. It has been found that the above problem can be solved in that cis-trans isomerization does not occur, and has already been disclosed in Japanese Patent Application No. 2009-209911 of Patent Document 15. However, the temperature at which the detachable group is desorbed from the precursor by applying energy is typically about 150 to 250 ° C. Therefore, there are still problems when using a substrate having low heat resistance such as some plastics. It was.
The present invention has been made in view of the current state of the prior art described above. It is easier to synthesize, has higher solubility in organic solvents, and has lower energy than before (hereinafter referred to as “external stimulus”). ) Using a novel π-electron conjugated compound precursor capable of leaving the leaving group, and applying an external stimulus such as heat to the precursor to produce a leaving component, 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 terminal olefin group which is unstable. Another object of the present invention is to provide an efficient method for producing a continuous thin film of a sparingly soluble π-electron conjugated compound by using this technique, and to apply the thin film to an organic electronic device (especially an organic thin film transistor).

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the inventions described in the following [1] to [14], and have reached the present invention. Hereinafter, the present invention will be specifically described.

[1] A releasability represented by the following general formula (II) from a coating film formed by applying a coating liquid 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 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、Ｑ_１乃至Ｑ_６上の任意の原子と、Ａ上の任意の原子とで共有結合を介して連結しているか、Ａ上の任意の原子と縮環している。Ｃは上記一般式（Ｉａ）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。
［式（Ｉ）、（Ｉａ）、（II）中、ＸおよびＹは水素原子もしくは脱離性置換基を表し、該ＸおよびＹのうち一方は脱離性置換基であり、他方は水素原子である。Ｑ_２乃至Ｑ_５はそれぞれ独立して水素原子、ハロゲン原子または、１価の有機基であり、Ｑ_１とＱ_６は水素原子、ハロゲン原子または、前記脱離性置換基以外の一価の有機基である。Ｑ_１乃至Ｑ_６は隣り合った基同士でそれぞれ結合して環を形成していてもよい。］

(Here, A is a π-electron conjugated substituent, and B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I). M is a natural number. , B is linked to any atom on Q _{1 to} Q ₆ and any atom on A in the above general formula (I) via a covalent bond, or is fused with any atom on A C has at least a partial structure of the structure represented by the above general formula (Ia).
[In the formulas (I), (Ia) and (II), X and Y represent a hydrogen atom or a detachable substituent, and one of the X and Y is a detachable substituent, and the other is a hydrogen atom. It is. Q _{2 to} Q ₅ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Q ₁ and Q ₆ are a monovalent organic other than a hydrogen atom, a halogen atom or the above-mentioned leaving substituent. It is a group. Q _{1 to} Q ₆ may be bonded to each other between adjacent groups to form a ring. ]

[2] The detachable substituent X or Y is an [ether group or acyloxy group] having 1 or more carbon atoms which may be substituted, and one of X and Y may be substituted. [1] The method for producing a film-like body according to [1], which is an [ether group or acyloxy group] having 1 or more carbon atoms and the other is a hydrogen atom.
[3] The application of the coating liquid is performed by a method selected from the group consisting of inkjet coating, spin coating, solution casting, and dip coating, [1] or [2] A method for producing a film-like body.
[4] The substituent A is (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound having two or more condensed rings, and (ii) the above (i) The ring according to any one of [1] to [3], which is a π-electron conjugated compound selected from the group consisting of compounds in which the rings are connected via a covalent bond A method for producing a film-like body.
[5] The elimination component represented by the general formula (II) desorbed from the compound A- (B) m is a hydrogen halide, an optionally substituted carboxylic acid, an optionally substituted alcohol, or carbon dioxide. Any one of the above, The method for producing a film-like body according to any one of [1] to [4].
[6] The compound A- (B) m is solvent-soluble, and the compound A- (C) m produced by elimination of the detachable substituent is solvent-insoluble [1] Thru | or the manufacturing method of the film-like body in any one of [5].
[7] A π-electron conjugated compound represented by A- (C) m by detaching a detachable substituent represented by the following general formula (II) from the π-electron conjugated compound precursor A- (B) m A method for producing a π-electron conjugated compound, characterized in that

（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、Ｑ_１乃至Ｑ_６上の任意の原子と、Ａ上の任意の原子とで共有結合を介して連結しているか、Ａ上の任意の原子と縮環している。Ｃは上記一般式（Ｉａ）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。
［式（Ｉ）、（Ｉａ）、（II）中、ＸおよびＹは水素原子もしくは脱離性置換基を表し、該ＸおよびＹのうち一方は脱離性置換基であり、他方は水素原子である。Ｑ_２乃至Ｑ_５はそれぞれ独立して水素原子、ハロゲン原子または、１価の有機基であり、Ｑ_１とＱ_６は水素原子、ハロゲン原子または、前記脱離性置換基以外の一価の有機基である。Ｑ_１乃至Ｑ_６は隣り合った基同士でそれぞれ結合して環を形成していてもよい。］

(Here, A is a π-electron conjugated substituent, and B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I). M is a natural number. , B is linked to any atom on Q _{1 to} Q ₆ and any atom on A in the above general formula (I) via a covalent bond, or is fused with any atom on A C has at least a partial structure of the structure represented by the above general formula (Ia).
[In the formulas (I), (Ia) and (II), X and Y represent a hydrogen atom or a detachable substituent, and one of the X and Y is a detachable substituent, and the other is a hydrogen atom. It is. Q _{2 to} Q ₅ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Q ₁ and Q ₆ are a monovalent organic other than a hydrogen atom, a halogen atom or the above-mentioned leaving substituent. It is a group. Q _{1 to} Q ₆ may be bonded to each other between adjacent groups to form a ring. ]

[8] The leaving substituent X or Y is an optionally substituted [ether group or acyloxy group] having 1 or more carbon atoms, and one of X and Y may be substituted. The method for producing a π-electron conjugated compound according to [7], which is an [ether group or acyloxy group] having 1 or more carbon atoms, and the other is a hydrogen atom.
[9] The substituent A is (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound in which two or more of the rings are condensed, and (ii) the above (i) The π-electron conjugate according to [7] or [8], characterized in that it is a π-electron conjugated compound selected from the group consisting of compounds in which the rings are linked via a covalent bond Of the production of the compound.
[10] The compound A- (B) m is solvent-soluble, and the compound A- (C) m produced by elimination of the detachable substituent is solvent-insoluble [7] Thru | or the manufacturing method of the pi-electron conjugated compound in any one of [9].
[11] The π-electron conjugated compound compound produced by the method according to any one of [7] to [10].

  According to the production method of the present invention, since a precursor of a novel solvent-soluble π-electron conjugated compound is used as a raw material, it is possible to suitably cope with a solution process, and in addition, external stimuli such as heat and light Π-electron conjugated system containing a benzene ring without the presence of unstable terminal substituents by eliminating the solvent-soluble substituents by the precursor substituent elimination reaction The compound can be produced simply and with high yield. In addition, the substituent elimination reaction of the π-electron conjugated compound precursor of the present invention has a lower energy than conventional π-electron conjugated compound precursors (for example, π-electron conjugated compound precursors based on a cyclohexene skeleton). (Low temperature). Moreover, after applying a solution containing a precursor of a π-electron conjugated compound and a solvent to form an organic film, an organic film made of a π-electron conjugated compound (including an organic semiconductor) is obtained by performing a substituent elimination reaction. Obtainable. By using such an organic film (including an organic semiconductor film), an organic electronic device (especially an organic thin film transistor) can be provided.

It is the schematic which shows the structural example of the organic thin-film transistor concerning this invention. It is sectional drawing of an example of the transistor array for driving a display image element. It is a figure showing an example of the transistor array for driving a display image element. In Example 26, it is a figure (TG-DTA) which shows the result of having observed the thermal decomposition behavior and phase change behavior of the compound (Ex. 1). In Example 27, it is a figure (TG-DTA) which shows the result of having observed the thermal decomposition behavior and phase change behavior of a compound (exact 2). 4 is a polarizing microscope photograph of a thin film produced using the compound (Act 1) or the compound (Act 2) of the present invention in Example 28. It is the electric current-voltage (IV) characteristic view of the organic thin-film transistor (FET element) of this invention produced in Example 29.

  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 the 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 the “π-electron conjugated compound precursor” having a specific solvent-soluble substituent to remove the specific substituent. It is characterized by producing the target film-like body and the π-electron conjugated compound by separating them. The “π-electron conjugated compound precursor” is represented by A- (B) m.
Here, A is a π-electron conjugated substituent, and B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I). m is a natural number. However, B is linked to any atom on A through a covalent bond at the positions of Q _{1 to} Q _{6 in} the above general formula (I), or is condensed with any atom on A. . By applying an external stimulus to this, the solvent-soluble substituent B leaves the specific leaving substituent X and X in the form of XY (a molecule in which X and Y are bonded), and instead a part thereof is a benzene ring. Is converted to the substituent C represented by the general formula (Ia) replaced with the compound film-like product represented by the π-electron conjugated compound A- (C) m, and the compound.

（Ｃは上記一般式（Ｉａ）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。
［式（Ｉ）、（Ｉａ）、（II）中、ＸおよびＹは水素原子もしくは脱離性置換基を表し、該ＸおよびＹのうち一方は脱離性置換基であり、他方は水素原子である。Ｑ_２乃至Ｑ_５はそれぞれ独立して水素原子、ハロゲン原子または、１価の有機基であり、Ｑ_１とＱ_６は水素原子、ハロゲン原子または、前記脱離性置換基以外の一価の有機基である。Ｑ_１乃至Ｑ_６は隣り合った基同士でそれぞれ結合して環を形成していてもよい。］

(C has at least a partial structure of the structure represented by the general formula (Ia).
[In the formulas (I), (Ia) and (II), X and Y represent a hydrogen atom or a detachable substituent, and one of the X and Y is a detachable substituent, and the other is a hydrogen atom. It is. Q _{2 to} Q ₅ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Q ₁ and Q ₆ are a monovalent organic other than a hydrogen atom, a halogen atom or the above-mentioned leaving substituent. It is a group. Q _{1 to} Q ₆ may be bonded to each other between adjacent groups to form a ring. ]

  First, the solvent-soluble substituent B and the substituent C after elimination conversion will be described.

The leaving substituent represented by X and Y in the formulas (I) and (II) is a hydrogen atom or an optionally substituted ether group or acyloxy group having 1 or more carbon atoms. At least one of them is a leaving substituent, that is, an optionally substituted ether group or acyloxy group having 1 or more carbon atoms, and the other is a hydrogen atom.
The ether group having 1 or more carbon atoms which may be substituted is derived from an alcohol such as a linear or cyclic aliphatic alcohol having 1 or more carbon atoms or an aromatic alcohol having 4 or more carbon atoms. Of ether groups. Further, a thioether group in which an oxygen atom in the ether is replaced with a sulfur atom can also be included. Specifically, for example, methoxy group, ethoxy group, propoxy group, butoxy group, isobutoxy group, pivaloyl group, pentoxy group, hexyloxy group, lauryloxy group, trifluoromethoxy group, 3,3,3-trifluoropropoxy group, Pentafluoropropoxy group, cyclopropoxy group, cyclobutoxy group, cyclohexyloxy group, trimethylsilyloxy group, triethylsilyloxy group, tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group, etc. Corresponding thioethers in which oxygen is replaced with sulfur are also included.
Examples of the acyloxy group having 1 or more carbon atoms which may be substituted 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, carbon Examples thereof include acyloxy groups derived from carboxylic acids and carbonic acid half esters such as aromatic carboxylic acids having a number of 4 or more. Moreover, thiocarboxylic acid in which the oxygen atom of the carboxylic acid is replaced with sulfur can also be included. Specifically, for example, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, pentanoyloxy, hexanoyloxy, lauroyloxy group, stearoyloxy group, trifluoroacetyloxy 3,3,3-trifluoropropionyloxy, pentafluoropropionyloxy, cyclopropanoyloxy, cyclobutanoyloxy, cyclohexanoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, pentafluorobenzoyloxy group Etc.
In addition, a carbonic acid ester derived from a carbonic acid half ester in which an oxygen atom or a sulfur atom is inserted between the carbonyl group of the acyloxy group exemplified above and an alkyl group or an aryl group can also be mentioned. In addition, corresponding acylthiooxy compounds and thioacyloxy compounds in which one or more of oxygen at the ether bond site and the carbonyl site are replaced with sulfur are also included.

  Some of the leaving substituents X and Y of the above concept are exemplified below.

Introduction of an optionally substituted ether group or acyloxy group (group having a leaving property) having 1 or more carbon atoms in the present invention, while maintaining high solubility in organic solvents and storage stability of the compound. In addition, the leaving group can be reliably eliminated with low energy (heating).
For example, as the leaving group, a substituted or unsubstituted ether group having 1 or more carbon atoms and a sulfonyloxy group having 1 or more carbon atoms may be introduced instead of an acyloxy group.
Examples of the optionally substituted sulfonyloxy group include sulfonyloxy groups derived from sulfonic acids such as linear or cyclic aliphatic sulfonic acids having 1 or more carbon atoms and aromatic sulfonic acids having 4 or more carbon atoms. It is done. Specifically, for example, methylsulfonyloxy group, ethylsulfonyloxy group, isopropylsulfonyloxy group, pivaloylsulfonyloxy group, pentanoylsulfonyloxy group, hexanoylsulfonyloxy group, trifluoromethanesulfonyloxy group, 3, 3 , 3-trifluoropropionylsulfonyloxy group, phenylsulfonyloxy group, p-toluenesulfonyloxy group, and the like, and a sulfonylthiooxy group in which the oxygen atom of the ether moiety is replaced with a sulfur atom can also be included.

In the general formulas (I) and (Ia) in the present invention, as the groups represented by Q _{1 to} Q ₆ , other than A which is a π-electron conjugated group, An atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a monovalent organic group (however, other than an ether group or acyloxy group having 1 or more carbon atoms which may be substituted in Q _{1 to} Q ₆₎ The monovalent organic group is an alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, arylthiooxy group, heteroaryloxy group. , Heterothioaryloxy group, alkoxyl group, thioalkoxyl group, aryloxy group, thioaryloxy group, cyano group, hydroxyl group, nitro group, carboxyl Group, a thiol group, and an amino group.

The alkyl group represents a linear or branched or cyclic substituted or unsubstituted alkyl group.
Examples thereof include alkyl groups [preferably substituted or unsubstituted alkyl groups having 1 or more carbon atoms [for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group]. 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, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group]], cycloalkyl group [preferably A substituted or unsubstituted alkyl group having 3 or more carbon atoms [eg, cyclopentyl group, cyclo Butyl group, a cyclohexyl group, pentafluoro cyclohexyl]] and the like.
In other monovalent organic groups described below, the alkyl group represents an alkyl group of the above concept.

  The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Examples thereof include an alkenyl group [preferably a substituted or unsubstituted alkenyl group having 2 or more carbon atoms and one or more double bonds of any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. [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 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 Group, 3-octenyl group, 4-octenyl group, 1,1,1-trifluoro-2-butenyl group]. ], A cycloalkenyl group [which includes one or more double bonds of any carbon-carbon single bond of the cycloalkyl group having 2 or more carbon atoms described above [for example, 1-cycloallyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group 4-cycloheptenyl group, 3-fluoro-1-cyclohexenyl group]. ] Etc. are mentioned. The alkenyl group may be any of stereoisomers such as trans (E) isomer and cis (Z) isomer, and may be a mixture composed of any ratio thereof. .

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 or more carbon atoms, wherein one or more triple bonds are formed from any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. Can be mentioned. Examples of such alkynyl groups include ethynyl group, propargyl group, trimethylsilylethynyl group, and triisopropylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 or more carbon atoms [for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-chlorophenyl, p-fluorophenyl, p-trifluoro. Phenyl, naphthyl, etc.].

  The heteroaryl group is preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound [for example, 2-furyl, 2-thienyl, 3-thienyl, 2-thienothienyl. , 2-benzothienyl, 2-pyrimidyl, etc.].

  The alkoxyl group and thioalkoxyl group are preferably substituted or unsubstituted alkoxyl groups and thioalkoxyl groups, and an oxygen atom or a sulfur atom is inserted at the bonding position of the alkyl group, alkenyl group, and alkynyl group exemplified above. Specific examples thereof include alkoxy groups or thioalkoxy groups.

  The aryloxy group and thioaryloxy group are preferably a substituted or unsubstituted aryloxy group and an arylthiooxy group, and an aryl or oxygen atom is inserted into the aryl group binding site exemplified above. Specific examples include an oxy group or a thioalkoxy group.

  The heteroaryloxy group and heterothioaryloxy group are preferably a substituted or unsubstituted heteroaryloxy group and heteroarylthiooxy group, and an oxygen atom or a sulfur atom at the binding site of the heteroaryl group exemplified above. Specific examples include those in which a heteroaryloxy group or a heteroarylthioaryloxy group is inserted.

  The amino group is preferably an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group [for example, an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group. Group, diphenylamino group], acylamino group [preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, [for example, formylamino, acetylamino, pivaloylamino group, lauroyl Amino, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group]], aminocarbonylamino group [preferably carbon-substituted or unsubstituted aminocarbonylamino group, [for example, carbamoylamino group] , N, N-Dime Le aminocarbonylamino group, N, N-diethylamino carbonyl amino group, a morpholinocarbonylamino group]], and the like.

As for the solvent-soluble substituent B and substituent C, the monovalent organic group represented by Q _{1 to} Q ₆ in the above general formulas (I) and (Ia) can be expressed in the above-mentioned range. Preferably, it is an aryl group or a heteroaryl group which may have a substituent, or adjacent groups form a cyclic structure. More preferably, the cyclic structure comprises an optionally substituted aryl group or heteroaryl group. As for the substituent B and the substituent C, examples of the bond of the ring and the condensed ring form include structures shown in the following I- (1) to I- (42).

  As described above, at least one of X and Y is an optionally substituted [ether group or acyloxy group] having 1 or more carbon atoms. Examples of such [ether group or acyloxy group] are as follows. It can have a structure represented by formula (III) or (IV).

ここで、Ｚは、上記一般式で表される構造式において、ｎ＝１の時は下記一般式（III−１）、（IV−１）のような構造となる。

Here, Z is a structural formula represented by the above general formula, and when n = 1, the structure is represented by the following general formulas (III-1) and (IV-1).

  In the structural formula represented by the above general formula, when n = 2, the following general formulas (III-2) and (IV-2) are obtained.

この構造式の場合には、一方のアシルオキシ基が前記ＸまたはＹの位置で置換され、他方のアシルオキシ基が同分子内もしくは他分子のＸ’またはＹ’（非表示）の位置で置換された構造を取り得る。

In this structural formula, one acyloxy group is substituted at the X or Y position, and the other acyloxy group is substituted within the same molecule or at the X ′ or Y ′ (not shown) position of another molecule. Can take a structure.

[In the above formula, Z represents an oxygen atom or a sulfur atom, which may be the same or different. R ₁ represents a hydrogen atom (except when n = 2 in the general formulas (III) and (IV)), a monovalent organic group or a divalent organic group. ]
Particularly preferably, a hydrogen atom [excluding when n = 2 in formulas (III) and (IV)], 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, more preferably a hydrogen atom [general formula (III), (Except when n = 2 in (IV))], a substituted or unsubstituted alkyl group. Most preferably, it is a substituted or unsubstituted alkyl group.

The leaving component XY includes the corresponding alcohol in which the —O— bond or —S— bond site of the substituent constituting the ether group or acyloxy group which may be substituted is cut and hydrogen is substituted at the terminal. Carboxylic acid and carbonic acid half ester are mentioned.
Examples of the alcohol include methanol, ethanol, propanol group, isopropanol, butanol, isobutanol, tertbutyl alcohol, pentanol, hexanol, trifluoromethanol, 3,3,3-trifluoropropanol, 3,3,3-trifluoro. Examples include fluoropropoxy group, pentafluoropropanol, cyclopropanol, cyclobutanol, cyclohexanol, trimethylsilanol, triethylsilanol, tert-butyldimethylsilanol, tert-butyldiphenylsilanol, etc., replacing oxygen at the ether bond site with sulfur Corresponding thiols are also included.
Examples of the carboxylic acid and carbonic acid half ester include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, lauric acid, stearic acid, trifluoroacetic acid, 3,3,3-trimethyl Fluoropropionic acid, pentafluoropropionic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid, p-methoxybenzoic acid, pentafluorobenzoic acid, methyl hydrogen carbonate, ethyl hydrogen carbonate, isopropyl hydrogen carbonate, hexyl hydrogen Examples include carbonate. Since these carbonic acid half esters are usually unstable, they may be decomposed to the corresponding alcohol (eg, methanol, ethanol, 2-propanol, hexanol) and carbon dioxide. Similarly, corresponding thiocarboxylic acids and thiocarbonic acid half esters in which oxygen at the ether bond site is replaced with sulfur are also included.

  For reference, examples of the substituted or unsubstituted sulfonyloxy group include those having a structure represented by the following general formula (V).

Examples of R ₂ in the general formula (V) include the same substituents as those described above and Q _{1 to} Q ₆ .
For example, 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, Examples thereof include a substituted or unsubstituted heteroaryl group and cyano group.
Examples of the leaving component XY include the corresponding sulfonic acid and thiosulfonic acid obtained by cleaving the —O— bond or the —S— bond site of the substituent constituting the sulfonyloxy group and replacing the terminal with hydrogen. , Methanesulfonic acid, ethanesulfonic acid, isopropylsulfonic acid, pivaloylsulfonic acid, pentanesulfonic acid, hexanoylsulfonic acid, toluenesulfonic acid, phenylsulfonic acid, trifluoromethanesulfonic acid, 3,3,3-trifluoropropionyl Examples thereof include sulfonic acid groups, and the corresponding thiosulfonic acids in which oxygen at the ether bond site is replaced with sulfur are also included.

The substituents R ₁ and R ₂ in the general formulas (III) to (V) are not particularly limited as long as they are within the above-mentioned range, but from the viewpoint of solvent solubility and film formability, these substituents are to some extent. It would be advantageous to reduce the intermolecular interaction and increase the affinity with the solvent, so if the volume change before and after the elimination of the substituent is too significant, the uniformity of the thin film in the elimination reaction There is a concern that problems will occur. Therefore, it is preferable that the substituent is as small as possible while maintaining appropriate solubility.
Although not yet known, R ₁ and R ₂ are electron-withdrawing substituents (for example, an alkyl group having a halogen or a group having a cyano group) that increases the degree of negative polarization of carbonyl oxygen. This is considered preferable in terms of increasing the efficiency of the elimination reaction.

Next, the π electron conjugated substituent A will be described. The substituent A may be any as long as it has a π-electron conjugated plane, and specifically, a benzene ring, a thiophene ring, a pyridine ring, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, Triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, furan ring, thiophene ring, selenophene ring, and silole ring are preferred, more preferably
(I) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound in which the rings are condensed with each other;
(Ii) π selected from a compound in which the rings of (ii) and (i) are linked via a covalent bond, and a combination selected from at least one selected from the group consisting of (i) and (ii) above Electron conjugated compounds,
In which the π electrons of each of the aromatic hydrocarbon ring or aromatic heterocycle are delocalized in the condensed ring or the entire connected ring by the interaction by the connection via the condensed ring and the covalent bond. Preferably there is.

The number of the aromatic hydrocarbon rings or aromatic heterocycles linked by the condensed ring or covalent bond is preferably 2 or more. Specific examples (general formulas are given for some examples) include naphthalene, anthracene, tetracene, chrysene, pyrene [the following general formula (Ar3)], pentacene, thienothiophene [the following general formula (Ar1)], thieno Dithiophene, triphenylene, hexabenzocoronene, benzothiophene [following general formula (Ar2)], benzodithiophene, [1] benzothieno [3,2-b] [1] benzothiophene [BTBT; following general formula (Ar4)] Dinaphtho [2,3-b: 2 ′, 3′-f] [3,2-b] thienothiophene [DNTT], benzodithienothiophene [TTPTT; the following general formula (Ar5)], naphthodithienothiophene [ TTTTT; condensed polycyclic compounds such as the following general formulas (Ar6) and (Ar7)], biphenyl, terphenyl, quarter Phenyl, bithiophene, terthiophene, aromatic oligomeric hydrocarbon ring and an aromatic hetero ring, phthalocyanines such as quaterthiophene, porphyrins, and the like.
Examples of the covalent bond here include a carbon-carbon single bond, a carbon-carbon double bond, a carbon-carbon triple bond, an oxyether bond, a thioether bond, an amide bond, and an ester bond. , Either a double bond or a triple bond.

Next, the bonding mode between the π-electron conjugated substituent A and the solvent-soluble substituent B will be described. B may be linked to any atom on A via a covalent bond, or may be condensed with any atom on A. Any substitution position other than the position of the leaving substituent on B can be substituted. Examples of the covalent bond here include a carbon-carbon single bond, a carbon-carbon double bond, a carbon-carbon triple bond, an oxyether bond, a thioether bond, an amide bond, and an ester bond. , Either a double bond or a triple bond.
In addition, the number of the soluble substituent B that is bonded or condensed to a certain π-electron conjugated substituent A via a covalent bond is naturally the number of atoms that can be substituted or condensed on A. Depends on. For example, an unsubstituted benzene ring can be bonded via a covalent bond at a maximum of 6 substitution positions, and can be condensed at a maximum of 6 positions. However, considering the size of the molecule of A itself, the number of substitutions depending on the solubility, the symmetry of the molecule, and the ease of synthesis, the lower limit of the soluble substituent of the present invention contained in one molecule is 2 or more. More preferred. On the other hand, if the number of substitutions is too large, the soluble substituents are sterically crowded, which is not preferable. Therefore, the upper limit is a sufficient number of substitutions depending on the symmetry of the molecule, ease of synthesis, and solubility. Considering 4 or less is preferable.

  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, and B is represented by the general formula (I). It is a solvent-soluble substituent having the structure represented as at least a partial structure. However, B is connected to any atom on Q1 to Q6 and any atom on A through a covalent bond in the above general formula (I), or condensed with any atom on A. ing. C has at least a partial structure of the structure represented by the general formula (Ia). 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 XY is eliminated from the solvent-soluble substituent B of the precursor by a substituent elimination reaction. And is converted to a substituent C having a benzene ring to obtain a π-electron conjugated compound A- (C) m.

The π-electron conjugated compound precursor of the present invention is characterized by having a detachable solvent-soluble substituent as described above and thereby making the solvent soluble.
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 lower the solubility from 1 wt% or more (solvent soluble) to 0.01 wt% or less, and from 0.5 wt% or more (solvent soluble) to less than 0.05 wt%. It is particularly preferable to reduce the solubility from 1.0 wt% or more to less than 0.1 wt%. And “solvent insoluble” means that the solvent has a solubility of less than 0.01 wt% in a state where the solvent is heated to reflux and then cooled to room temperature, preferably 0.005 wt% or less. More preferably, it is 0.001 wt% or less.

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 actually used solvent and temperature, for example, solubility in THF, toluene, chloroform, or methanol. (25 ° C.). However, the solvent used in the present invention is not limited thereto.
Before and after the conversion by the elimination reaction of X and Y, that is, from the π electron conjugated compound precursor having the partial structure represented by the general formula (I), the compound partial structure represented by the general formula (Ia) The solubility of these compounds is greatly changed by the conversion to a compound having a compound (referred to as “specific compound” or “organic semiconductor compound”). That is, when different films are successively laminated on a specific compound, it is difficult to be attacked by the solvent of the solution used for forming the laminated film, so that the manufacturing process of organic electronic devices such as organic thin film transistors, organic EL, organic solar cells, etc. Useful in.

Examples of the specific structure of A- (B) m that can be obtained by combining the above-described π-electron conjugated substituent A and solvent-soluble substituent B include the following compound groups (Exemplary Compound 1 to Exemplary Compound 42). The π electron conjugated compound precursor in the present invention is not limited to these. Moreover, it can be easily inferred that a solvent-soluble substituent has a plurality of stereoisomers of a leaving substituent, and the following compounds include a mixture of isomers having different steric configurations.
The storage stability of the π-electron conjugated compound precursor of the present invention means that the detachable soluble substituent is not unintentionally removed until the conversion treatment is performed. The form may be solid or may be dissolved in a solvent to form ink or waste, or a film formed from the ink.
As an index for prescribing the degree of storage stability, a solid or ink is left at a constant temperature (generally about 20 degrees) under a certain condition (humidity 50%, under light shielding) for a certain period (for example, one month). It can be determined by analyzing the later state. What is necessary is just to quantify the molecules that have been unintentionally desorbed and converted.
Since the elimination reaction is due to energy application, it is possible to enhance the storage stability by storing it under a low temperature (for example, 0 ° C. to −100 ° C.), light shielding, or an inert atmosphere. Preferably, unintentional elimination of the leaving group does not occur at -40 ° C. under light shielding (eg, 0.5% or more of new impurities are not detected after storage from a precursor having an LC purity of 99.5%). More preferably, it does not occur at 0-5 ° C, most preferably it does not occur at 5-40 ° C.

By applying energy such as heat (applying or applying an external stimulus) to the precursor A- (B) m, a desorption reaction described later occurs, and the substituents X and Y are eliminated, thereby π electrons A film-like body containing the conjugated compound A- (C) m and the compound can be obtained.
Specific examples of A- (C) m (referred to as a specific compound) produced from A- (B) m shown in the specific examples are shown in the following specific compound 1 to specific compound 29 below. The π electron conjugated compound is not limited to these.

[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, for example, coating on a substrate (support) such as plastics, metal, silicon wafer, glass, etc. The precursor represented by general formula (I) is converted into the compound represented by general formula (Ia) (specific compound) and the compound represented by general formula (II) (leaving component) by applying energy. To do.

  The compound represented by the general formula (I) has a plurality of isomers having different steric arrangements of substituents, all of which are converted into the specific compound represented by the general formula (Ia) and eliminated. The components remain the same.

X and Y, which are groups leaving from the compound represented by the general formula (I), are defined as leaving substituents, and XY formed by combining them is defined as a leaving component. 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 of the desorbing component is preferably 500 ° C. or less at atmospheric pressure (1013 hPa). Considering the ease of removal out of the system and the decomposition / sublimation temperature of the π-conjugated compound produced, the boiling point is 400 ° C. or less. More preferably, it is 300 ° C. or less.

The following is an example of the case where X in the general formula (I) is an optionally substituted acyloxy group, and Y and Q ₁ and Q ₆ are hydrogen atoms. Show. The conversion by the leaving reaction of the π-electron conjugated compound precursor of the present invention is not limited to this.

In the case of the above example, by applying energy (heating), the carboxylic acid having the alkyl chain represented by the general formula (VIII) is eliminated from the cyclohexadiene ring structure represented by the general formula (VI) as the elimination component. To a specific compound having a structure containing a benzene ring represented by the general formula (VII). When the heating temperature exceeds the boiling point of the carboxylic acid, the carboxylic acid quickly becomes a gas.
An outline of the mechanism by which the elimination component is eliminated from the compound represented by the general formula (VI) is shown by the following reaction formula (scheme). In the following reaction mechanism, the elimination mechanism of the elimination component from the cyclohexadiene ring structure of the present invention is conversion from the following general formula (VI-a) to the following general formula (VII-a). To supplement the explanation, the elimination mechanism in the case of a cyclohexene ring [the following general formula (IX)] is also shown. In the following formula, R ₃ represents a substituted or unsubstituted alkyl group.

As shown in the above reaction formula, in the case of the cyclohexene ring represented by the general formula (VI-a), by taking a transition state of a six-membered ring, the hydrogen atom on the β-carbon is transferred onto the oxygen atom of the carbonyl. The 1,5-rearrangement causes a concerted elimination reaction, whereby the carboxylic acid compound is eliminated and converted from a cyclohexene ring structure to a benzene ring structure represented by the general formula (VII-a).
In the case of a compound having a cyclohexene structure having two acyloxy groups [general formula (IX)], the elimination reaction is considered to proceed in two steps. First, one carboxylic acid is eliminated and the general formula (VI-a) is eliminated. It becomes the cyclohexadiene ring structure represented by these.
At this time, the activation energy required to desorb one molecule of carboxylic acid from the disubstituted product represented by the general formula (IX) is the same as that of the 1 substituted product represented by the general formula (VI-a). Since it is sufficiently larger than that required for desorbing the molecule, the reaction proceeds rapidly in two steps, and is converted to a structure represented by the general formula (VII-a). That is, in the case of the above reaction formula, the monosubstituted product represented by the general formula (VI-a) cannot be isolated in the reaction system.
Here, even when there are a plurality of stereostereoisomers due to the difference in the positional relationship between the substituents (acyloxy group and hydrogen, etc.), the above reaction proceeds although the reaction rate is different.
As inferred from the above reaction formula, if an active mono-substituted product can be synthesized, it is advantageous because less energy is required for the elimination reaction than the cyclohexene ring represented by the general formula (VI). It is. That is, the cyclohexadiene ring structure of the present invention can reliably perform the elimination reaction of the detachable substituent with lower energy (external stimulus) than before.

  The lowering of the elimination reaction of the cyclohexadiene skeleton is not limited to acyloxy groups, and similar effects can be seen with ether groups and the like. In conventional cyclohexene skeletons such as ether groups, the energy required for elimination reaction is high and not suitable for use. However, by applying the skeleton of the present invention, the energy is reduced and the same as in acyloxy groups. It became possible to use.

  In the above reaction formula, the extraction and transfer of hydrogen atoms on the β carbon is the first stage of the reaction, so the reaction is considered to occur more easily as the force of attracting hydrogen atoms of oxygen atoms is stronger. The degree varies depending on, for example, the alkyl chain on the acyloxy group side, and also varies by changing the oxygen atom to a chalcogen atom such as sulfur, selenium, tellurium, polonium or the like, which is also a group 16 element.

Examples of the energy applied (applied) for carrying out this elimination reaction include heat, light, and electromagnetic waves. From the viewpoint of reactivity, yield, and post-treatment, thermal energy or light energy is desirable, especially thermal energy. Is preferred. 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 heating is often required from the viewpoint of reaction rate and reaction rate. 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.

The heating temperature for carrying out the elimination reaction can be in the range of room temperature (approximately 25 ° C.) to 500 ° C., and the lower limit temperature is the upper limit temperature in consideration of the thermal stability of the material and the boiling point of the elimination component. Then, in view of energy efficiency, abundance of unconverted molecules, decomposition of the compound after conversion, sublimation, etc., a range of 40 ° C. to 500 ° C. is preferable, and thermal stability during the synthesis of the π-electron conjugated compound precursor is further improved. Considering it, it is more preferably in the range of 60 ° C to 500 ° C, particularly preferably in the range of 80 ° C to 400 ° C.
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 π-electron conjugated compound precursor, it is usually 0.5 minutes to 120 minutes, preferably 1 minute to 60 minutes, and 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.

In the elimination reaction of the detachable substituent, the acid or base acts as a catalyst, and conversion at a lower temperature is possible. Although these usage methods are not particularly limited, they may be added to the π-electron conjugated compound precursor as it is, dissolved in an arbitrary solvent and added as a solution, or vaporized in the atmosphere. A heat treatment may be performed, or 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 light irradiation.
Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, 3,3,3-trifluoropropionic acid, formic acid, phosphoric acid, 2-butyloctanoic acid, and the like. it can.
As the photoacid generator, 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 can be used. .
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, diazabicyclo Amidines such as nonene can be used.
As the photobase generator, carbamates, acyl oximes, ammonium salts and the like can be used.
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 performed in the air with or without the above catalyst. However, in order to eliminate side effects such as oxidation and the influence of moisture, a system of further desorbed components is used. In order to promote the exclusion to the outside, it is desirable to carry out under an inert gas atmosphere or under reduced pressure.

Regarding the method for forming an acyloxy group as a detachable substituent, an alcohol described later is reacted with a carboxylic acid chloride or a carboxylic acid anhydride, or a carbon atom is exchanged between a halogen atom and a carboxylic acid silver or a carboxylic acid-quaternary ammonium salt. In addition to the method for obtaining acid esters, a method for obtaining carbonate esters by reacting phosgene and alcohol, a method for obtaining xanthate esters by reacting alkyl iodide after adding carbon disulfide to alcohol, tertiary amine and peroxidation Examples include, but are not limited to, a method of obtaining amine oxide by reacting hydrogen or carboxylic acid, a method of obtaining selenoxide by reacting orthoselenocyanonitrobenzene with alcohol, and the like.
The ether group can also be adjusted by a method in which a base is allowed to act on an alcohol and subsequently an alkyl halide, a halogenated alkylsilane, or the like (Williamson ether synthesis method), but is not limited thereto. It is not a thing.

[3. Method for producing π-electron conjugated compound precursor]
As described above, the π-electron conjugated compound precursor of the present invention is characterized by having a cyclohexadiene skeleton and a detachable substituent (the entire structural site is defined as a soluble substituent B). .
The so-called soluble substituent B portion of the structure composed of this cyclohexadiene skeleton and a leaving substituent is not rigid and sterically bulky, so that the crystallinity is poor, and a molecule having such a structure has solubility. It is good and has a property that an amorphous film with low crystallinity or amorphousness can be easily obtained when applied using a solution in which a π-electron conjugated compound precursor is dissolved.

Next, a method for forming an ether group and an acyloxy group in the cyclohexadiene skeleton will be described in detail with an example.
A method for forming an ether group or acyloxy group in the cyclohexadiene skeleton can be derived from a compound having a cyclohexen-1-one skeleton as represented by the following general formula (X). The compound represented by the general formula (X) can be produced by a conventionally known method and can be used as a raw material. However, in view of the form of the elimination reaction of the present invention, 2 next to the ketone. It is preferable that each group has one or more hydrogen atoms.

[In formula (X), Q _{2 to} Q ₆ are the same as the range defined in formula (I). ]

  Next, as shown in the following reaction formula, the 1-position ketone group of the compound represented by the general formula (X) is reduced to an alcohol using a reducing agent to obtain a compound represented by the general formula (XI). .

[In formulas (X) and (XI), Q _{2 to} Q ₆ are the same as the range defined in formula (I). ]

As a method of the above reduction reaction, hydride reduction using sodium borohydride, lithium aluminum hydride or the like as a reducing agent, or catalytic reduction using a metal catalyst such as nickel, copper, ruthenium, platinum, palladium, etc. and hydrogen. However, hydride reduction is more preferable in view of functional group selectivity and ease of reaction.
Various organic solvents can be used as the solvent used in the reduction reaction, and alcohols such as methanol and ethanol are particularly preferable from the viewpoint of reaction rate.
The reaction temperature is usually about 0 ° C., but from room temperature to the reflux temperature of the solvent can be suitably used depending on the reactivity.

  Subsequently, as shown in the following reaction formula, the compound represented by the general formula (XI) obtained by the above reaction is converted into a compound represented by the general formula (XII) to protect the OH group of the alcohol form. Examples of the protective group include acetyl group, methyl group, trimethylsilyl group, and benzyl group. These are not particularly limited. However, since the reaction conditions described below are basic, the number of protective groups that can be deprotected under basic conditions is the number of steps. This is preferable in terms of a decrease in.

[In formulas (XI) and (XII), Q _{2 to} Q ₆ are the same as the range defined in formula (I). R is an OH protecting group. ]
Examples of the OH protecting group include an acetyl group, a methyl group, a trimethylsilyl group, and a benzyl group.

In the above reaction formula, an example of using as a group that can be deprotected under basic conditions will be described.
A carboxylic acid ester is formed by reacting with 1 equivalent of carboxylic acid anhydride (for example, acetic anhydride) in the presence of a base (XII-1). As the base, tertiary amines such as pyridine and triethylamine can be preferably used, and these can be added in excess to be used as a solvent.
As the solvent, in addition to the above, a large number of reactive organic solvents such as dichloromethane and tetrahydrofuran can be used.

  Subsequently, as shown in the following reaction formula, the 4-position of the general formula (XII-1) obtained by the above reaction is selectively halogenated using 1 equivalent of a halogenating agent to give a general formula (XIII) The compound represented is obtained.

[In formulas (XII-1) and (XIII), Q _{2 to} Q ₆ are the same as the range defined in formula (I). Ac is an acetyl group. ]

In the above reaction formula, an iodine atom, a bromine atom and a chlorine atom are preferred from the reactivity of the subsequent step, and a bromine atom is particularly preferred. Examples of the brominating agent include N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, and the like, and it is preferable to perform these in the presence of 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. The reaction temperature can be suitably used from room temperature to the reflux temperature of the solvent.
In this step, a plurality of stereoisomers may be generated depending on the reaction conditions. Specifically, a racemic mixture and a meso form may be obtained in an arbitrary ratio depending on the configuration of a carboxylic acid ester group bonded to a cyclohexene ring and a bromo group. Although it is not particularly necessary to separate them, they can be separated by recrystallization or chromatography using an optically active fixed layer.

  Subsequently, as shown in the following reaction formula, the compound represented by the general formula (XIII) obtained by the above reaction is formed with a double bond formed by elimination of a bromo group using a base and a deprotection group. Conversion to a hydroxyl group is performed to obtain a compound represented by the general formula (XIV).

［式（XIII）、（XIV）中、Ａｃはアセチル基である。］

[Ac is an acetyl group in the formulas (XIII) and (XIV). ]

  In the above reaction formula, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide and the like can be used as the base. A strong base is particularly preferred because the hydroxyl group can be deprotected simultaneously. The solvent to be used is not particularly limited, but alcohol solvents such as methanol and ethanol are preferable from the viewpoint of reactivity.

  Regarding the synthesis of the above alcohol, a polycyclic aromatic compound having an active K region (shown by a circled region in the figure below) is relatively easily hydroxylated in the active region using a method different from the above. Can be introduced and substituted with a leaving group. Examples of such polycyclic aromatic compounds include picene, benzopicene and the like in addition to phenanthrene, chrysene, pyrene and benzopyrene shown in the figure below.

Hereinafter, in the above general formula (XIV), phenanthrene having a structure in which two benzene rings are condensed at positions (Q ₂ , Q ₃ ) and (Q ₄ , Q ₅ ) is used as an example. The introduction will be described.

  First, as shown in the following reaction formula, the K region (9th and 10th positions) of phenanthrene is epoxidized using an oxidizing agent to obtain an epoxy derivative represented by the general formula (XV).

As the method of the above K region epoxidation reaction, organic compounds such as m-perbenzoic acid, hydrogen peroxide, peracetic acid, oxone, dimethyldioxirane, and sodium hypochlorite aqueous solution are used as well as the oxidants in the conventional epoxidation. Inorganic peroxides can also be used. In view of ease of handling, m-perbenzoic acid, hydrogen peroxide, sodium hypochlorite aqueous solution and the like are preferable.
The solvent is not particularly limited as long as it dissolves the compound well and does not oxidize itself. For example, dichloromethane, chloroform, carbon tetrachloride, benzene, water and the like can be used. Particularly preferred are dichloromethane, chloroform and water.
When an oxidizing agent such as an aqueous sodium hypochlorite solution is used, it is preferable to carry out the reaction in a two-phase system in which a compound is dissolved in an organic phase and a phase transfer catalyst is added. As the phase transfer catalyst, a so-called surfactant can be used, and examples thereof include a quaternary ammonium salt or a sulfonium salt as a main component.
The reaction temperature is usually about 0 ° C., but from room temperature to the reflux temperature of the solvent can be suitably used depending on the reactivity.

  First, as shown in the following reaction formula, the epoxy derivative represented by the general formula (XV) is reduced with a reducing agent to obtain the target alcohol compound represented by the general formula (XVI).

As a method for the above reduction reaction, hydride reduction using sodium borohydride, lithium aluminum hydride (LAH), diisobutylaluminum hydride (DIBAL) or the like as a reducing agent, nickel, copper, ruthenium, platinum, palladium However, hydride reduction is more preferable in view of functional group selectivity and ease of reaction. Among hydride reducing agents, a strong reducing agent to some extent is suitable for reducing epoxy. Examples include lithium aluminum hydride (LAH), diisobutylaluminum hydride (DIBAL), and the like.
Although various organic solvents can be used as the solvent used in the reduction reaction, it is required not to react with the reducing agent, and ether solvents are particularly preferable. Examples include diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane and the like.
The reaction temperature is usually about 0 ° C., but from room temperature to the reflux temperature of the solvent can be suitably used depending on the reactivity.

  Subsequently, as shown in the following reaction formula, a carbonic acid half ester such as a carboxylic acid anhydride, a carboxylic acid chloride, or an alkyl chloroformate is added to the compound (alcohol) represented by the general formula (XIV) obtained by the above reaction. The compound represented by the general formula (XVII) (the target product in which the 1-position is acyloxylated) can be obtained by reacting a group with a base.

[In formulas (XIV) and (XVII), Q _{2 to} Q ₆ are the same as the range defined in formula (I). Acy is an acyl group. ]

Examples of the carbonic acid half esters such as carboxylic acid anhydride and carboxylic acid chloride and alkyl chloroformate used in the above reaction include carboxylic acids (for example, acetic acid, butyric acid, valeric acid, propionic acid, pivalic acid, caproic acid, stearic acid, And compounds derived from trifluoroacetic acid and 3,3,3-trifluoropropionic acid). In the above reaction formula, pyridine, triethylamine, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride and the like can be used as the base. In the case of acylation, it is not always necessary to be a strong base, as long as it is possible to trap hydrochloric acid generated in the reaction. Further, as the solvent used, various organic solvents such as pyridine and triethylamine, dichloromethane, tetrahydrofuran, toluene, which also serve as the base can be used, but in order to prevent reaction rate and side reactions, the solvent is as much as possible. It is preferable to use a dehydrated one.
The reaction temperature may be from room temperature to the solvent reflux temperature, but is preferably 50 ° C. or lower, and most preferably room temperature (near 25 ° C.) or lower in order to prevent side reactions such as elimination reaction. That is.
In the above process, if a halogenated alkyl or halogenated alkylsilane or sulfonic acid derivative is used in place of the carboxylic acid derivative, a skeleton having an alkyl ether group, a silyl ether group, or a sulfonyloxy group can be easily obtained by a known method. Construction can also be achieved.
However, in the case of alkyl halides and halogenated silyl ethers, it is better to use strong bases such as sodium hydride, sodium hydroxide and potassium carbonate instead of weak bases such as triethylamine and pyridine.

The soluble substituent B obtained by synthesizing according to the above reaction formula is condensed with the π electron conjugated compound A by various conventionally known methods to form a π electron conjugated compound having a condensed ring structure. A precursor (fused ring compound) can be synthesized. When this is used as a π-electron conjugated compound precursor, for example, in the case of heteroacenes, Am. Chem. Soc. 2007, 129, pp 2224-2225, and the like.
The detailed reaction formula (scheme) is shown by giving a specific example below.

The starting material 1-acyloxy-6-iodo-1,2-dihydronaphthalene used in the above reaction formula can be synthesized according to the synthesis example of the present invention.
As a first step, a Grineer exchange reaction between iodine atoms and a Grineer reagent is performed. Because of the extremely low temperature and the high reactivity of iodine, a Grineer exchange reaction occurs selectively and a Grineer reagent is obtained. Formylation is performed by adding a formylating agent such as dimethylformamide or morpholine to the Grineer reagent.
The second step is ortho trithiolation of the formyl group. Since the amine, lithium, and formyl group to be added simultaneously form a complex, the ortho position (position 7 of 1,2-dihydronaphthalene) is selectively lithiated without impairing other functional groups. This is similarly converted to SMe by adding dimethyl sulfide.
Subsequently, in the third stage, McMurry coupling reaction between formyl groups is performed. The reaction is carried out in the presence of zinc and titanium tetrachloride. Thereby, formyl groups couple with each other to form an olefin structure.
In the final stage, a ring closure reaction with iodine is performed. Iodine is added to the double bond site, subsequently reacts with the SMe group, and is eliminated in the form of MeI, whereby two thiophene rings are formed, and the desired condensed ring compound can be obtained.

  In the case of pentacene, J.A. Am. ChemSoc. , 129, 2007, pp. The ring formation reaction in the case of phthalocyanines can be carried out in accordance with the method described in “Phthalocyanine-Chemistry and Function” edited by Masayoshi Shirai and Nagao Kobayashi (IPC, 1997). 1 to 62, Ryo Takahashi, Keiichi Sakamoto, and Eiko Okumura, “Phthalocyanine as a functional dye” (IPC, 2004), pages 29 to 77 can be used in the same manner. Porphyrins In this case, it can be performed according to the method described in JP-A-2009-105336.

In addition, in the π-electron conjugated compound precursor of the present invention, as a method for linking the above-described solvent-soluble substituent (B in the following general formula) by covalent bond with another skeleton, a method by Suzuki coupling reaction, Stille Various coupling reactions represented by a coupling reaction method, a Kumada coupling reaction, a Negishi coupling reaction method, a Hiyama coupling reaction method, a Sonogashira reaction method, a Heck reaction method, a Wittig reaction method, etc. The well-known method performed using is illustrated.
Among these, a method using a Suzuki coupling reaction or a Stille coupling reaction is particularly preferable from the viewpoint of reactivity and yield that the derivatization of the intermediate is easy. In addition to the above, in the formation of the carbon-carbon double bond, a method by Heck reaction, Wittig reaction, and the like are also preferable. In the formation of a carbon-carbon triple bond, in addition to the above, the Sonogashira reaction is particularly preferable.
Below, the example which connects a carbon-carbon bond by a Suzuki coupling reaction and a Stille coupling reaction is given to the following.

The reaction is carried out using a combination of a halogen compound and a trifluorotriflate compound represented by the following general formulas (XVIII) and (XIX) or a boronic acid derivative and an organotin derivative. However, when the compounds represented by the general formulas (XVIII) and (XIXI) 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.
And it is manufactured by adding a base to the said mixture only in the case of Suzuki coupling reaction, and making it react in presence of a palladium catalyst.

  [In Formula (XVIII), A is the above-mentioned π-electron conjugated substituent, D is a halogen atom (representing a chlorine atom, a bromine atom or an iodine atom), a triflate (trifluoromethanesulfonyl) group, a boronic acid or The ester or organotin functional group is shown. l is an integer of 1 or more. ]

  [In the formula (XIX), B is the above-mentioned solvent-soluble substituent, D is a halogen atom (representing a chlorine atom, a bromine atom or an iodine atom), a triflate (trifluoromethanesulfonyl) group, or a boronic acid, its ester or organotin Indicates a functional group. k is a natural number. )

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

As the organotin functional group in the general formulas (XVIII) and (XIX), a derivative having an alkyltin group such as a SnMe ₃ group or a SnBu ₃ group can be used. These can be easily obtained by replacing a hydrogen or halogen atom at a desired position with lithium or a grinder reagent using an organometallic reagent such as n-butyllithium, and then quenching with trimethyltin chloride or tributyltin chloride.
The boronic acid derivative is synthesized from a halogenated derivative using bis (pinacolato) diboron that is thermally stable and easily handled in air in addition to boronic acid, or the boronic acid is protected with a diol such as pinacol. A boronic acid ester derivative synthesized by this method may be used.

  As described above, either substituent A or B may be a halogen and triflate, or a boronic acid derivative and an organotin derivative. However, in terms of ease of derivatization and reduction of side reactions, substituent A is preferred. Often it is 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, a strong base such as Ba (OH) ₂ , K ₃ PO ₄ , or NaOH is 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 (PPh ₃ ) ₂ ], tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ], dichlorobis (acetonitrile) palladium [Pd (CH ₃ CN ₂ Cl ₂ ], dichlorobis (benzonitrile) palladium _{[Pd (PhCN) 2 Cl 2} ], dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) _Cl 2], dichloro [1,1-bis (Jifeniruho ) Ferrocene] palladium [Pd (dppf) _Cl 2], dichlorobis (tricyclohexylphosphine) palladium _{[Pd [P (C 6 H 11} ) 3] 2 Cl 2 ], dichlorobis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₂ Cl ₂ ], tris (dibenzylideneacetone) dipalladium [Pd ₂ (dba) ₃ ], bis (dibenzylideneacetone) palladium [Pd (dba) ₂ ] and the like, but tetrakis (triphenylphosphine) Palladium [Pd (PPh ₃ ) ₄ ], dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) Cl ₂ ], dichlorobis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₂ Cl ₂ ] Is preferred. Arbitrariness.

  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 reaction temperature should be kept below the boiling point of the solvent. preferable. In addition, it is preferable from the viewpoint of yield to suppress to a temperature at which the elimination reaction occurs or less, specifically, a range of room temperature to 150 ° C. is preferable, a range of room temperature to 120 ° C. is particularly preferable, and a range of room temperature to 120 ° C. is most preferable. It is in the range of 100 ° C.
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.

  As described above, a π-electron conjugated compound precursor represented by the following general formula (XX) is obtained.

[In Formula (XX), A is the same as Formula (XVIII) and B is the same as Formula (XIX), respectively, and m is an integer of 1 or more. ]

The resulting π-electron conjugated compound precursor is used after removing impurities such as the catalyst used in the reaction, unreacted raw materials, and boronate 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.
A material having excellent solubility has fewer restrictions on these purification methods, and as a result, has a positive effect on device characteristics.

In order to make the π-electron conjugated compound precursor obtained by the above-described manufacturing method into a thin film, for example, a solution containing the π-electron conjugated compound precursor and a solvent (may be in the form of ink or the like) is used. Film formation by spin coating method, casting method, dipping method, ink jet method, doctor blade method, screen printing method, or π electron conjugated compound itself after heat conversion is formed by vacuum deposition, sputtering, etc. A known film forming method can be used. By these film forming methods, it is possible to produce a good thin film free from cracks and excellent in strength, toughness, durability and the like.
Further, by applying energy (applying external stimulus) to the film of the π-electron conjugated compound precursor A- (B) m of the present invention applied by the film forming method, it is represented by the general formula (I). By removing the compound (leaving component) represented by the general formula (II) from the soluble leaving group B and converting it to C represented by the general formula (Ia), π electrons Since it is possible to form an organic semiconductor film made of a conjugated compound A-C (m) (an organic semiconductor material or the like can be used as an application), it can be used for various functional elements such as a photoelectric conversion element, a thin film transistor element, and a light emitting element. It can be suitably used as a material.

[4. Application of π-electron conjugated compounds to devices]
The π-electron conjugated compound (here, an organic semiconductor compound) produced from the π-electron conjugated compound precursor of the present invention can be used for an electronic device, for example. As an example of an electronic device, a device that has two or more electrodes and controls the current flowing between the electrodes or the voltage generated by electricity, light, magnetism, or a chemical substance, 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, or an optical element such as a photodiode or a phototransistor that generates a photocurrent can be used.

  Examples of electronic devices suitable for applying the π-electron conjugated compound precursor of the present invention and the π-electron conjugated compound (here, an organic semiconductor compound) produced therefrom include an organic thin film transistor, that is, an organic field effect transistor (OFET). Can be mentioned. Hereinafter, this FET will be described in detail.

"Transistor structure"
1A to 1D are schematic views showing structural examples of organic thin film transistors according to the present invention. The organic semiconductor layer (1) of the organic thin film transistor according to the present invention contains an organic semiconductor compound [AC (m)] converted by applying energy to the π-electron conjugated compound precursor of the present invention. The organic thin film transistor of the present invention includes a third electrode on a spatially separated first electrode (source electrode (2)), second electrode (drain electrode (3)) and a support (substrate) (not shown). An electrode (gate electrode (4)) is provided, and 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. It is important that the amount of current flowing between the source electrode (2) and the drain electrode (3) can be greatly modulated by the application state of the voltage. This means that a large current flows when the transistor is driven, and no current flows when the transistor is not driven.

  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”
As described above, the π-electron conjugated compound precursor of the present invention is used as an organic semiconductor precursor, and is dissolved in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene, and xylene. ) And coating the solution on a support to form a thin film made of an organic semiconductor precursor, and then applying energy to this film to convert it to an organic semiconductor film. .

[Ink composition, solvent]
The solvent used in the ink composition can be determined as follows.
For example, a thin film can be formed by dissolving in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene, and xylene and coating on a support. That is, the solvent for the coating liquid containing the precursor can be appropriately selected according to the purpose, but it is preferable that the boiling point is 500 ° C. or less because it is easy to remove. However, the higher the volatility, the better. Those having a boiling point of 50 ° C. or higher are preferred. Although not 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, specifically as the solvent, the precursor A- (B) m has, for example, a polar carboester group as a leaving group or an ether group having affinity for methanol, ethanol, isopropanol, etc. Alcohols, glycols such as ethylene 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 and dimethyl In addition to nitrogen-containing organic solvents such as amine and triethylamine, polar (water-miscible) solvents such as cellosolve (registered trademark) such as methyl cellosolve and ethyl cellosolve, toluene, xylene, Of hydrocarbons such as carbon dioxide, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate Such ester solvents, and 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.
Further, the coating solution may further contain a volatile or self-decomposable acid or base material for accelerating the decomposition of the carboester group without impairing the achievement of the object of the present invention. 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.

Further, as described above, the π-electron conjugated compound precursor of the present invention has an ether group or acyloxy group which may be substituted with a cyclohexadiene structure. Unfortunately, molecules having this structure have good solubility and low crystallinity when applied from a solution, or an amorphous film can be easily obtained.
The methods for producing these thin films include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, ink jet, dispensing, screen printing, offset printing, Examples thereof include printing methods such as letterpress printing and flexographic printing, and soft lithography methods such as microcontact printing, and a method combining a plurality of these methods can also be used.
And according to material, a suitable solvent is selected from the said suitable film forming method and the said solvent.
Furthermore, the organic semiconductor material itself after heat conversion can be formed into a vapor phase by a vacuum deposition method or the like.

  Among the above-mentioned printing / coating methods, the droplet coating method represented by the ink jet method drops the droplet only at a predetermined position on the substrate, so that the material can be used without waste. Since the unnecessary material removal process for unnecessary portions is not necessary, the process can be simplified.

As conditions for stable ejection, it is necessary to examine at least two points: the drying speed of the solvent and the solute concentration of the ink with respect to the solubility of the solute.
Regarding the drying speed, a solvent having an excessively high vapor pressure, that is, a relatively low boiling point, causes a problem that the solute is precipitated by the rapid solvent drying around the nozzle of the inkjet, and the nozzle is clogged. Inadequate manufacturing. Therefore, it is generally considered that a solvent having a high boiling point is suitable for the ink jet method, but in the present invention, it is desirable to include a solvent having a boiling point of at least 150 ° C. or higher. More desirably, it includes a solvent having a boiling point of at least 200 ° C. or higher.
The solubility of the solute with respect to the ink solvent is desirably a solvent that dissolves at least 0.1% by weight or more of the organic semiconductor material used in the present invention. More desirably, the solvent dissolves 0.5% by weight or more. Examples of the solvent satisfying the above include cumene, cymene, mesitylene, 2,4-trimethylbenzene, propylbenzene, butylbenzene, amylbenzene, 1,3-dimethoxybenzene, nitrobenzene, benzonitrile, N, N-dimethylaniline, N, N-diethylaniline, tetralin, 1,5-dimethyltetralin, cyclohexanone, methyl benzoate, ethyl benzoate, propyl benzoate and the like can be mentioned.

  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, a film having 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 nm to 100 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, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by inkjet, 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 can 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 and electrode interface modification"
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 electrode 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.

Specific examples of organic molecular films include octyltrichlorosilane, octadecyltrichlorosilane, hexamethylenedisilazane, phenyltrichlorosilane, benzenethiol, trifluorobenzenethiol, perfluorobenzenethiol, and perfluorodecanethiol. A ring agent is mentioned. 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 thin film transistor of the present invention is stably driven even in the atmosphere, but is protected as necessary for protection from mechanical destruction, protection from moisture and gas, or protection required for device integration. Layers can also be provided.

"Applied devices"
The π electron conjugated compound precursor and the organic semiconductor of the present invention are useful because various organic electronic devices such as a photoelectric conversion element, a thin film transistor element, and a light emitting element can be produced.
The organic thin film transistor of the present invention described above can be suitably used as an element for driving various conventionally known display image elements such as liquid crystal, electroluminescence, electrochromic, electrophoresis, and so on. It is possible to produce a display called “paper”.

  The display device of the present invention includes, for example, a liquid crystal display element in a liquid crystal display device, an organic or inorganic electroluminescence display element in an EL display device, and a display element such as an electrophoretic display element in an electrophoretic display device as one display pixel. A plurality of display elements are arranged in a matrix in the X and Y directions. The display element includes the organic thin film transistor of the present invention as shown in FIG. 2 as a switching element for applying voltage or supplying current to the display element. The display device of the present invention includes a plurality of the switching elements corresponding to the number of the display elements, that is, the number of display pixels.

  The display element includes, in addition to the switching element, for example, a substrate, an electrode such as a transparent electrode, a polarizing plate, a color filter, and the like. However, these components are not particularly limited and may be used depending on the purpose. Can be appropriately selected, and conventionally known ones can be used.

  When the display device forms a predetermined image, for example, the switching elements arbitrarily selected from the switching elements arranged in a matrix as shown in FIG. 3 are used as the corresponding display elements. By configuring the switch to be turned on or off only when voltage is applied or current is supplied, and to be turned off or on at other times, display of the display device can be performed at high speed and with high contrast. As an image display operation in the display device, an image or the like is displayed by a conventionally known display operation.

  For example, in the case of the liquid crystal display element, an image or the like is displayed by controlling the molecular arrangement of the liquid crystal by applying a voltage to the liquid crystal. In the case of the organic or inorganic electroluminescent display element, an image or the like is displayed by supplying a current to a light emitting diode formed of an organic or inorganic film to cause the organic or inorganic film to emit light. In the case of the electrophoretic display element, for example, a voltage is applied to white and black colored particles charged to different polarities, and the particles are electrophoresed between electrodes in a predetermined direction to generate an image or the like. Is displayed.

The display device can be manufactured by a simple process such as coating and printing of the switching element, and can use a substrate that cannot withstand high-temperature processing such as a plastic substrate or paper, and can be a large-area display. However, the switching element can be fabricated with energy saving and low cost.
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.

First, specific compound intermediates related to the compounds used in Examples and Comparative Examples were synthesized.
Moreover, the identification of the compound in the following synthesis example and an Example is NMR spectrum [JNM-ECX (brand name) 500MHz, JEOL make], mass spectrometry [GC-MS, GCMS-QP2010 Plus (brand name), Shimadzu Corporation make. ], Accurate mass spectrometry [LC-TofMS, Alliance-LCT Premier (trade name), manufactured by Waters], elemental analysis [(CHN) (CHN recorder MT-2, manufactured by Yanagimoto Seisakusho), elemental analysis (sulfur) (ion chromatography) An anion analysis system: DX320 (trade name, manufactured by Dionex)].

[Synthesis Example 1]
[Synthesis of specific compound intermediate 1]
<Synthesis of Compound (2)>
Compound (2) was synthesized according to the following reaction formula (scheme).

The compound of the above formula (1) used as it was purchased from SIGMA Aldrich.
In a 500 mL beaker, put the compound of formula 1 (20 g, 119.0 mmol) and 15% HCl (96 mL), and maintain an aqueous sodium nitrite solution (9.9 g, 143.0 mmol + water) while maintaining the temperature at 5 ° C. or lower under ice cooling. 42 mL) was gradually added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 30 minutes, an aqueous potassium iodide solution (23.7 g, 143.0 mmol + 77 mL of water) was added at once, the ice bath was removed and the mixture was stirred for 2.5 hours, and then at 60 ° C. Heated for 0.5 hour until evolution stopped. 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: ethyl acetate / hexane = 9/1) to obtain a pale orange solid. Furthermore, recrystallization from 2-propanol gave Compound (2) as pale orange crystals (yield 11.4 g, yield 35.2%).

The analysis results of compound (2) are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.13 (quant, 2H, J = 5.7 Hz), 2.64 (t, 2H, J = 6.3 Hz), 2.92 (T, 2H, J = 6.0 Hz), 7.66 (d, 1H, J = 8.0 Hz),, 7.67 (s, 1H), 7.72 (d, 1H, J = 8 .0 Hz)
Melting point: 74.0-75.0 ° C
Mass spectrometry: GC-MS m / z = 272 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (2).

<Synthesis of Compound (3)>
Compound (3) was synthesized according to the following reaction formula (scheme).

Compound (2) (4.1 g, 15 mmol) and methanol (100 mL) were placed in a 200 mL round bottom flask, and sodium borohydride (850 mg, 22.5 mmol) was gradually added at 0 ° C. under ice cooling. The mixture was stirred for 3 hours while maintaining the temperature. Excess sodium borohydride was neutralized with dilute hydrochloric acid, saturated brine was added, and the mixture was extracted 5 times with ethyl acetate (50 mL). The extract was washed once with ammonium chloride (100 mL), then twice with brine (100 mL), and dried by adding sodium sulfate. The filtrate was concentrated to obtain compound (3) as a pale red solid (yield 3.93 g, yield 95.5%). The product was used in the next reaction as it was without further purification.
The analysis results of compound (3) are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.71 (d, 1H, J = 5.8 Hz), 1.84 to 2.02 (m, 4H), 2.65-2. 71 (m, 1H,), 2.75-2.81 (m, 1H,), 4.72 (d, 1H, J = 4.6 Hz), 7.17 (d, 1H, J = 8. 0 Hz),, 7.47 (s, 1 H), 7.52 (d, t ₁ H, J ₁ = 8.0 Hz, J ₂ = 1.2 Hz)
Mass spectrometry: GC-MS m / z = 274 (M +)
Melting point: 82.0-84.0 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (3).

<Synthesis of Compound (4)>
Compound (4) was synthesized according to the following reaction formula (scheme).

Compound (3) (3.70 g, 13.5 mmol) and N, N-dimethylaminopyridine (hereinafter referred to as DMAP, 10 mg) were placed in a 50 mL round-bottomed flask and replaced with argon gas, and then dehydrated pyridine (8.1 ml) ), Acetic anhydride (6.2 ml) was added, and the mixture was stirred at room temperature for 6 hours.
50 mL of water was added to the reaction solution, and the mixture was extracted 5 times with ethyl acetate (20 mL). The combined organic layers were washed 3 times with dilute hydrochloric acid (100 ml), followed by 2 times with saturated sodium bicarbonate solution (100 ml), and finally The extract was washed twice with saturated brine (100 ml) and dried over magnesium sulfate. The filtrate was concentrated to obtain compound (4) as a brown liquid (yield 4.28 g, yield 100%). The product was used in the next reaction as it was without further purification.

The analysis result of compound (4) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.76-1.83 (m, 1H,), 1.89-2.10 (m, 1H), 2.07 (s, 3H) , 2.67-2.73 (m, 1H,), 2.79-2.84 (m, 1H,), 5.93 (t, 1H, J = 5.2 Hz), 7.01 (d , 1H, J = 8.6 Hz), 7.49 (d, 1H, J = 2.3 Hz), 7.52 (s, 1H)
Mass spectrometry: GC-MS m / z = 316 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (4).

<Synthesis of Compound (5)>
Compound (5) was synthesized according to the following reaction formula (scheme).

In a 100 mL round-bottom flask, compound (4) (4.27 g, 13.5 mmol), azobisisobutyronitrile (hereinafter AIBN, 25 mg), carbon tetrachloride (100 mL), N-bromosuccinimide (hereinafter NBS, 2. 64 g, 14.8 mmol) was added, and after substitution with argon gas, the mixture was gently heated to 80 ° C., stirred as it was for 1 hour, and cooled to room temperature.
The precipitate was filtered, and the filtrate was concentrated under reduced pressure to obtain a light yellow solid. This was purified by silica gel column chromatography (solvent: ethyl acetate / hexane = 8/2) to obtain compound (5) as a pale red oil (yield 4.9 g, yield 92.0%). . Compound (5) was obtained as a 10: 7 mixture of cis and trans isomers.

The analysis results of compound (5) are shown below.
Accurate mass spectrometry: LC-MS m / z = 393.907 (100.0%), 395.904 (97.3%)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (5).

<Synthesis of Compound (6)>
Compound (6) was synthesized according to the following reaction formula (scheme).

  Compound (5) (4.2 g, 10.6 mmol) was placed in a 500 mL round-bottomed flask and purged with argon gas. Then, THF (300 mL) was added, and sodium methoxide-methanol solution (25 wt. %, 24 mL) was added and stirred at that temperature for 6 hours. Water (300 mL) was added, extracted four times with ethyl acetate (100 mL), washed twice with saturated brine (100 mL), dried over sodium sulfate, and the filtrate was concentrated to give a brown liquid. This was subjected to column purification to obtain compound (6) as colorless crystals (yield 1.2 g, yield 41.0%).

The analysis results of compound (6) are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.70 (d, 1H, J = 3.4 Hz), 2.58-2.61 (m, 2H), 4.76 (q, 1H, J = 6.3 Hz), 6.04 (q, 1H, J = 5.2 Hz), 6.47 (d, 1H, J = 9.8 Hz), 7.13 (d, 1H, J = 8.1 Hz), 7.47 (d, 1H, J = 1.7 Hz), 7.57 (J ₁ = 8.1 Hz J ₂ = 1.7 Hz)
Mass spectrometry: GC-MS m / z = 272 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (6).

<Synthesis of Compound (7-1)>
Compound (7-1) was synthesized according to the following reaction formula (scheme).

  Compound (6) (680 mg, 2.5 mmol) and DMAP (15.3 mg, 0.125 mmol) were placed in a 50 mL round-bottomed flask and replaced with argon gas. Then, pyridine (15 mL) was added, and the mixture was cooled to 0 ° C. under ice-cooling. At 0 ° C., hexanoyl chloride (370 mg, 2.75 mmol) was added dropwise, and the mixture was stirred at the same temperature for 3 hours. Water was added to the reaction solution, followed by extraction three times with ethyl acetate (50 mL), and the 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 brown liquid. The liquid was dissolved in ethyl acetate / hexane (95/5), passed through a silica gel pad having a thickness of 3 cm, and the filtrate was concentrated to obtain a compound (7-1) as a colorless liquid (yield 560 g, yield 60). .5%).

The analysis result of the compound (7-1) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.2 Hz), 1.21-1.30 (m, 4H), 1.54-1. 60 (m, 2H), 2.23 (td, 2H, J 1 = 7.5 Hz J 2 = 2.3 Hz), 2.58-2.62 (m, 2H), 5.95 (t, 1H, J = 5.2 Hz), 6.03 (quint, 1H, J = 4.6 Hz), 6.48 (d, 1H, J = 9.8 Hz), 7.10 (d, 1H, J = 8.0 Hz), 7.48 (d, 1H, J = 1.7 Hz), 7.54 (dd, 1H, J1 = 8.0 Hz, J2 = 1.8 Hz)
Mass spectrometry: GC-MS m / z = 370 (M +), 254 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (7-1).

<Synthesis of Compound (7-2)>
Compound (7-2) was synthesized according to the following reaction formula (scheme).

  Compound (6) (680 mg, 2.5 mmol) and THF (15 mL) were placed in a 50 mL round-bottom flask and replaced with argon gas, and then sodium hydride (3.0 mmol, 72. 0 mg) was added and the mixture was stirred at the same temperature for 30 minutes. Methyl iodide (3.0 mmol, 426 mg) was added dropwise, and the mixture was stirred at the same temperature for 1 hour. Water was added to the reaction solution, and the aqueous layer was extracted three times with ethyl acetate (50 mL). The combined organic layer was washed with saturated brine and dried over magnesium sulfate. The filtrate was concentrated to give a brown liquid. The liquid was dissolved in ethyl acetate / hexane (90/10), passed through a 3 cm thick silica gel pad, and the filtrate was concentrated to obtain compound (7-2) as a colorless oily solid (yield 607 mg, yield). 85.0%).

The analysis result of the compound (7-2) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.57-2.61 (m, 2H), 3.38 (s, 3H), 5.90 (t, 1H, J = 5.2) Hz), 6.03 (quint, 1H, J = 4.6 Hz), 6.48 (d, 1H, J = 9.8 Hz), 7.10 (d, 1H, J = 8.0 Hz) 7.48 (d, 1H, J = 1.7 Hz), 7.54 (dd, 1H, J = 1.8 Hz)
Mass spectrometry: GC-MS m / z = 286 (M +), 254 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (7-1).

<Synthesis of Compound (7-3)>
Compound (7-3) was synthesized according to the following reaction formula (scheme).

  Compound (6) (680 mg, 2.5 mmol) and DMAP (15.3 mg, 0.125 mmol) were placed in a 50 mL round-bottomed flask and replaced with argon gas. Then, pyridine (15 mL) was added, and the mixture was cooled to 0 ° C. under ice-cooling. At ° C, amyl chloroformate (414 mg, 2.75 mmol) was added dropwise and stirred at the same temperature for 5 hours. Water was added to the reaction solution, followed by extraction three times with ethyl acetate (50 mL), and the 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 brown liquid. The liquid was dissolved in ethyl acetate / hexane (95/5), passed through a 3 cm thick silica gel pad, and the filtrate was concentrated to obtain a compound (7-3) as a colorless liquid (yield 535 mg, yield 55). .5%).

The analysis result of the compound (7-3) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.2 Hz), 1.21-1.30 (m, 4H), 1.60-1. 65 (m, 2H), 2.58-2.62 (m, 2H), 4.15-4.17 (m, 2H), 5.94 (t, 1H, J = 5.2 Hz), 6 .02 (quint, 1H, J = 4.6 Hz), 6.50 (d, 1H, J = 9.8 Hz), 7.08 (d, 1H, J = 8.0 Hz), 7.47 (D, 1H, J = 1.7 Hz), 7.53 (dd, 1H, J = 1.8 Hz)
Mass spectrometry: GC-MS m / z = 386 (M +), 254 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (7-3).

<Synthesis of Compound (7-4)>
Compound (7-4) was synthesized according to the following reaction formula (scheme).

Compound (6) (680 mg, 2.5 mmol) and THF (20 mL) were placed in a 50 mL round-bottom flask, and replaced with argon gas. (300 mg, 2.75 mmol) was added dropwise, and the mixture was stirred at the same temperature for 1 hour. The ice bath was removed, the temperature was returned to room temperature, and the mixture was further stirred for 7 hours.
Water was added to the reaction solution, followed by extraction three times with ethyl acetate (50 mL). The organic layer was washed with saturated brine and dried over magnesium sulfate. The filtrate was concentrated to give a brown liquid. The liquid was dissolved in ethyl acetate / hexane (95/5), passed through a 3 cm thick silica gel pad, and the filtrate was concentrated to obtain compound (7-3) as a colorless oily solid (yield 688 mg, yield). 80.0%).

The analysis result of the compound (7-4) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.04 (s, 9H), 2.50-2.55 (m, 2H), 5.15 (t, 1H, J = 5.2) Hz), 6.02 (quant, 1H, J = 4.6 Hz), 6.53 (d, 1H, J = 9.8 Hz), 7.07 (d, 1H, J = 8.0 Hz) , 7.44 (d, 1H, J = 1.7 Hz), 7.54 (dd, 1H, J = 1.8 Hz)
Mass spectrometry: GC-MS m / z = 344 (M +), 254 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (7-4).

<Synthesis of Compound (7-5)>
Compound (7-5) was synthesized according to the following reaction formula (scheme).

  In the synthesis of compound (7-1), the stoichiometric ratio was synthesized and purified in the same manner except that 2-butyloctanoyl chloride was used instead of caproic acid chloride, and compound (7-5) was obtained as a pale yellow liquid. (Yield 1.33 g, Yield 97.8%).

The analysis result of the compound (7-5) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.74-0.83 (m, 6H), 1.10-1.32 (m, 12H), 1.36-1.43 (m , 2H), 1.50-1.60 (m, 2H), 2.27-2.32 (m, 1H), 2.58-2.62 (m, 2H), 5.95 (t, 1H) , J = 5.2 Hz), 6.03 (quint, 1H, J = 4.6 Hz), 6.48 (d, 1H, J = 9.8 Hz), 7.10 (d, 1H, J = 8.0 Hz), 7.48 (d, 1H, J = 1.8 Hz), 7.54 (dd, 1H, J1 = 8.0 Hz, J2 = 1.8 Hz)
Mass spectrometry: GC-MS m / z = 454 (M +), 254 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (7-5).

[Synthesis Example 2]
[Synthesis of Compound Intermediate 2]
<Synthesis of Compound (8)>
Compound (8) was synthesized according to the following reaction formula (scheme).

  Thieno [3,2-b] thiophene (2.81 g, 20.0 mmol) was placed in a well-dried 200 mL round bottom flask, and after argon substitution, dehydrated tetrahydrofuran (hereinafter abbreviated as 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 interior 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 potassium fluoride 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)>
Compound (9) was synthesized according to the following reaction formula (scheme).

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, and after argon substitution, 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 inside 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 potassium fluoride 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, 18 H), 7.41 (s, 2 H), 8.27 (s, 2 H)
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)>
Compound (10) was synthesized according to the following reaction formula (scheme).

2-Bromophenylacetic acid (5.12 g, 23.8 mmol), toluene (20 mL) and methanol (10 mL) as raw materials are put into a 100 mL round bottom flask, and a 2M hexane solution (12.5 mL) of trimethylsilyldiazomethane is added thereto. The solution was gradually added dropwise and stirred for 15 minutes. Excess trimethylsilyldiazomethane was quenched with acetic acid, and the reaction solution was concentrated under reduced pressure using an evaporator. Toluene was added to the residue, and the solution was concentrated again through a 3 cm thick silica gel pad to obtain Compound (10) as a pale yellow liquid.
(Yield 5.1 g, 94%)

The analysis results of Compound 10 are shown below.
Accurate mass spectrometry: LC-TofMS m / z = 227.966 (actual value), 227.979 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 10.

<Synthesis of Compound (11)>
Compound (11) was synthesized according to the following reaction formula (scheme).

1,200-dibromopyrene (2.5 g, 6.9 mmol) was placed in a well-dried 200 mL round bottom flask, purged with argon, dehydrated THF (120 mL) was added, and an acetone-dry ice bath was added. The mixture was cooled to −78 ° C., n-butyllithium (2.15 eq, 9.1 mL (1.6 M hexane solution), 14.9 mmol) was added dropwise over 5 minutes, and the mixture was stirred for 2 hours. At −78 ° C., 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.2 eq, 15.3 mmol, 3.1 mL) was added in one portion and at that temperature. After stirring for 1 hour, the temperature in the reaction system was raised to room temperature, and further stirred for 2 hours.
Aqueous ammonium chloride (50 mL) and water (100 mL) were added to quench, and toluene was added to separate the organic layer. The aqueous layer was extracted twice with toluene, and the combined organic layers were washed with saturated brine, subsequently dried over sodium sulfate, and the filtrate was concentrated to obtain a yellow solid. This was dissolved in a minimum amount of toluene, and the filtrate was concentrated through a silica gel column (3 cm) to obtain a pale yellow solid. This was recrystallized from toluene / acetonitrile to obtain Compound (11) as colorless crystals. (Yield 2.2g, 70%)

The analysis results of compound (11) are shown below.
Accurate mass spectrometry: LC-TofMS m / z = 454.244 (actual value), 454.249 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (11).

<Synthesis of Compound (12)>
Compound (12) was synthesized according to the following reaction formula (scheme).

  In a 300 mL three-necked flask, 1,4-benzenedimethanol (15.7 g, 94.6 mmol), iodine (19.2 g, 75.7 mmol), iodic acid (8.3 g, 47.3 mmol), chloroform (50 mL) , Acetic acid (50 mL) and concentrated sulfuric acid (10 mL) were added and replaced with argon gas. Then, it stirred at 80 degreeC for 3 hours. Thereafter, an additional ¼ mol of iodine and iodic acid was added and stirred for 1 hour. After cooling to room temperature, the precipitated target product was collected by filtration with a PTFE filter. A sodium hydrogen sulfite aqueous solution was added to the residue, followed by extraction with chloroform. After washing with brine, the solvent was concentrated to obtain a brown solid. By combining with the filtrate, compound (12) was obtained as a brown solid. (Yield 28.0 g, 71%)

The analysis results of compound (12) are shown below.
Mass spectrometry: GC-MS m / z = 458 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (12).

<Synthesis of Compound (13)>
Compound (13) was synthesized according to the following reaction formula (scheme).

Compound (12) (4.18 g, 10 mmol) and 30 mL of acetone were added to a 500 mL eggplant flask and stirred at room temperature. 6.18 mL of Jones reagent (1.94M) was added thereto and heated under reflux conditions. While confirming that the color turned green, an additional 30.9 mL of Jones reagent was added. After confirming that the reaction had sufficiently progressed by TLC, the temperature was returned to room temperature, 20 mL of 2-propanol was added and the mixture was further stirred for 30 minutes. The precipitate was filtered and washed thoroughly with water to obtain a white solid (13). (Yield 3.16 g, 71%)
When confirmed by FTIR, CO stretching of the carboxylic acid was observed in the vicinity of 1750 cm ⁻¹ .

The analysis result of the compound (13) is shown below.
Mass spectrometry: GC-MS m / z = 446 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (13).

<Synthesis of Compound (14)>
Compound (14) was synthesized according to the following reaction formula (scheme).

THF (300 ml) and zinc powder (17.23 ml, 0.263 mol) were placed in a 500 ml four-necked flask and cooled to 0 ° C. with an ice bath. Thereto, titanium tetrachloride (50.0 g, 0.263 mol) was appropriately added and refluxed for 1.5 hours. After cooling to room temperature, 2-bromobenzaldehyde (10.16 ml, 0.0879 mol) was added and refluxed for 5 hours.
After cooling to room temperature, the reaction solution was added to a saturated aqueous sodium hydrogen carbonate solution (500 ml) and stirred, and further ethyl acetate (500 ml) was added and stirred overnight. Celite filtration was performed to separate insoluble matters, and the resulting solution was extracted with ethyl acetate. The organic layer was washed with water saturated brine, and then the organic layer was dried over magnesium sulfate. Magnesium sulfate was filtered off and recrystallized with ethyl acetate to obtain Compound (14). (Yield 7.0 g, 54% yield)

The analysis result of the compound (14) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 7.15 (t, 2H, J = 5.5 Hz), 7.34 (t, 2H, J = 5.5 Hz), 7.40 (s, 2H,), 7.60 (dd, 2H, J1 = 7.9 Hz, J2 = 1.5 Hz), 7.73 (dd, 2H, J1 = 7.9 Hz, J2 = 1.5 Hz)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 14.

<Synthesis of Compound (15)>
Compound (15) was synthesized according to the following reaction formula (scheme).

  Cyclohexane (400 ml), compound (14) and iodine (0.22 g, 0.0017 mol) were placed in a 500 ml four-necked flask. A low-pressure mercury lamp (manufactured by Ushio) was irradiated for 24 hours. The precipitated solid was filtered off and washed with cyclohexane. Recrystallization from toluene gave compound (15). (Yield 1.7 g, Yield 57%)

The analysis result of compound (15) is shown below.
¹ H-NMR (CDCl 3, TMS) σ: 7.53 (dd, 2H, J ₁ = 8.1 Hz, J ₂ = 7.7 Hz), 7.94 (d, 2H, J = 8.1 Hz), 8 .31 (s, 2H,), 8.67 (d, 2H, J = 7.7 Hz)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (15).

<Synthesis of Compound (16)>
Compound (16) was synthesized according to the following reaction formula (scheme).

  Toluene (60 ml), vinyltributyltin (1.47 ml, 0.0050 mol) and compound (15) (0.77 g, 0.0023 mol) were placed in a 200 ml four-necked flask. The mixture was stirred for 45 minutes while bubbling with argon gas. Tetrakistriphenylphosphine palladium (0.23 g, 0.00020 mol) was added and refluxed for 4 hours. The mixture was cooled to room temperature, poured into a saturated aqueous potassium fluoride solution (100 ml) and stirred, and further ethyl acetate (100 ml) was added and stirred. Celite filtration was performed, insolubles were filtered off, and the resulting solution was extracted with ethyl acetate. The organic layer was washed with water saturated brine, and then the organic layer was dried over magnesium sulfate. Magnesium sulfate was filtered off and recrystallized from ethyl acetate to obtain Compound (16). (Yield 0.43 g, Yield 82%).

The analysis result of the compound (16) is shown below.
¹ H-NMR (CDCl 3, TMS) σ: 5.52 (dd, 2H, J ₁ = 17.4 Hz, J ₂ = 1.4 Hz), 5.81 (dd, 2H, J ₁ = 10.9 Hz, J ₂ = 1.4 Hz), 7.55 (dd, 2H, J ₁ = 17.4 Hz, J ₂ = 10.9 Hz), 7.64 (dd, 2H, J ₁ = 8.0 Hz, J ₂ = 7. 2 Hz), 7.74 (d, 2H, J = 7.2 Hz), 8.10 (s, 2H,), 8.68 (d, 2H, J = 8.0 Hz)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (16).

<Synthesis of Compound (18)>
Compound (18) was synthesized according to the following reaction formula (scheme).

  In a 2 L round bottom flask, non-patent literature Advanced Materials, 2009, 21, 213-216. Compound (17) dithieno [2,3-d; 2 ′, 3′-d ′] benzo [1,2-b; 4,5-b ′] dithiophene (12.7 g, 42 mmol) synthesized by the method described After replacing with argon gas, dehydrated chloroform (600 mL) and acetic acid (600 mL) were added, and the internal temperature of the container was kept at 0-3 ° C. using an ice bath. Next, N-iodosuccinimide (20.8 g, 92.4 mmol) was gradually added under light shielding. After stirring for 1 hour, the ice bath was removed, the temperature was returned to room temperature, and stirring was continued overnight. The precipitate was collected by filtration, and the precipitate was washed with a saturated aqueous sodium hydrogen sulfite solution followed by ethanol, toluene, and ethanol. The precipitate was dried under vacuum to give a pale yellow solid. This contained a small amount of the 1-substituted product in addition to the 2-substituted compound (20), but it was not separated at this stage and used as it was without purification in the following reaction. (Yield 21.5 g, Yield 92.3%)

The analysis result of the compound (18) is shown below.
Mass spectrometry: GC-MS m / z = 554 (M +), 428 (M + -I)
From the above analysis results, it was confirmed that the synthesized compound (18) was the main product.

<Synthesis of Compound (19)>
Compound (19) was synthesized according to the following reaction formula (scheme).

A 300 mL round bottom flask was charged with compound (22) (2.55 g, 4.60 mmol) and copper iodide (43.7 mg, 0.23 mmol), and replaced with argon gas, followed by tetrahydrofuran (hereinafter THF, 100 mL). ), Diisopropylethylamine (6.5 mL), dichlorobis (triphenylphosphine) palladium (II) (hereinafter, PdCl ₂ (PPh ₃ ) ₂ 97.2 mg, 0.138 mmol) are added, and trimethylsilylacetylene ( 1.4 mL, 10.12 mmol) was added slowly. The mixture was stirred at room temperature overnight to obtain a red uniform solution. Water (200 mL) and toluene (100 mL) were added and the organic layer was separated. The aqueous layer was extracted three times with toluene (50 mL), and the combined organic layer was washed with saturated brine (100 mL) and dried over sodium sulfate. The filtrate was concentrated and subjected to column purification (stationary phase: silica gel, mobile phase: toluene) to obtain a red solid. This was recrystallized from toluene / acetonitrile to obtain a compound (19) as yellow needle crystals. (Yield: 1.35 g, Yield: 59.1%)

The analysis result of the compound (19) is shown below.
Mass spectrometry: GC-MS m / z = 494.0 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (19).

<Synthesis of Compound (20)>
Compound (20) was synthesized according to the following reaction formula (scheme).

  Compound (19) (2.3 g, 4.65 mmol), THF (100 mL) and methanol (30 mL) were placed in a 300 mL round bottom flask, and potassium hydroxide solution (1.2 g dissolved in 15 mL of water) was added. The mixture was stirred as it was for 3 hours, water (100 mL) and methanol (100 mL) were added, and the deposited precipitate was collected by filtration. The precipitate was washed with water and methanol in this order, and dried under vacuum to obtain Compound (20) as a brown solid. (Yield 1.62 g, 99.5%)

The analysis result of the compound (20) is shown below.
Mass spectrometry: GC-MS m / z = 349.9 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (20).

<Synthesis of Compound (21)>
Compound (21) was synthesized according to the following reaction formula (scheme). The starting material 2,7-diiodo-9,10-dihydrophenanthrene was obtained from Chem. Mater. , 2008, 20 (20), pp 6289-6291, and the one synthesized.

  In a 300 mL round bottom flask, 2,7-diiodo-9,10-dihydrophenanthrene (8.21 g, 19 mmol), AIBN (0.38 mmol, 62.4 mg), NBS (22.8 mmol, 4.06 g) Then, carbon tetrachloride (150 mL) was taken and stirred at reflux temperature for 2 hours under an argon atmosphere. After cooling to room temperature, the precipitate was collected by filtration, washed with water, followed by hot water, followed by methanol, and dried under reduced pressure to obtain compound (21) as a pale yellow solid. (Yield 7.41 g, Yield 91%)

The analysis result of the compound (21) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 7.63 (s, 2H), 7.91 (dd, 2H, J ₁ = 8.5 Hz, J ₂ = 1.7 Hz), 8 .26 (d, 2H, J = 1.7 Hz), 8.35 (d, 2H, J = 8.5 Hz)
Mass spectrometry: GC-fMS m / z = 430 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (21).

<Synthesis of Compound (22)>
Compound (22) was synthesized according to the following reaction formula (scheme).

  Compound (21) (14 mmol, 6.02 g) and chloroform (300 mL) were added to a 2 L round bottom flask, and cooled with a water bath (20 ° C.), sodium hypochlorite aqueous solution (manufactured by Kanto Chemical Co., Ltd., chlorine concentration 5) %, PH 8-10, 750 mL) and sodium tetrabutylammonium hydrogen sulfate (7 mmol, 2.38 g) were added, and the mixture was stirred at 20 ° C. for 5 hours. Ice water (400 mL) was added, the organic layer was separated, and the aqueous layer was extracted twice with chloroform. The combined organic layers were washed with water followed by saturated brine and dried over potassium carbonate. The filtrate was concentrated and subjected to column purification (stationary phase: silica gel, mobile phase: toluene) to obtain compound (22) as a pale yellow solid. (Yield 1.25g, Yield 20.0%)

The analysis result of the compound (22) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 4.50 (s, 2H), 7.45 (dd, 2H, J1 = 8.6 Hz, J2 = 2.3 Hz), 7.65 (D, 2H, J = 2.3 Hz), 7.97 (d, 2H, J = 8.6 Hz)
Mass spectrometry: GC-fMS m / z = 446 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (22).

<Synthesis of Compound (23)>
Compound (23) was synthesized according to the following reaction formula (scheme).

  A compound (22) (4.46 g, 10 mmol) and diethyl ether (200 mL) were placed in a 300 mL round bottom flask, and replaced with argon gas. Then, lithium aluminum hydride (12 mmol, 455 mg) was added, and the mixture was stirred under reflux for 4 hours. Went. Water (0.5 mL) was added followed by 1.0 N aqueous sodium hydroxide solution (0.5 mL), followed by water (1.5 mL), and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure to obtain an oily solid. This was used for the next reaction without purification.

  In a separate 200 mL round bottom flask, the oily solid (4.48 g), THF (30 mL), pyridine (5 mL), DMAP (0.5 mmol, 61 mg) were taken, and caproic acid chloride (1.1 eq, 11 mmol, 1.48 g) was gradually added dropwise and stirred at 0 ° C. for 1 hour, the ice bath was removed and the mixture was stirred at room temperature for 6 hours. A 10% aqueous sodium hydrogen carbonate solution (100 mL) was added and stirred for 30 minutes, chloroform (50 mL) was added, and the organic layer was separated. The aqueous layer was extracted twice with chloroform, and the combined organic layer was washed with 10% aqueous sodium hydrogen carbonate solution, followed by water and saturated brine, and dried over sodium sulfate. The filtrate was concentrated to obtain compound (23) as a pale yellow oil. (Yield 3.55g, 65%)

The analysis result of the compound (23) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.2 Hz), 1.21-1.30 (m, 4H), 1.54-1. 60 (m, 2H), 2.20-2.23 (m, 2H), 3.05 (d, 2H), 6.05 (t, 1H), 7.45-7.95 (m, 6H)
Mass spectrometry: GC-fMS m / z = 546 (M +), 430 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (23).

[Synthesis Example 3]
<Synthesis of Compound (Comparative 1)>
A compound (Comparative 1) was synthesized according to the following reaction formula (scheme).
Intermediate iodotetralin derivative (7 ′) and compound (Comparative 1) were synthesized according to the method described in Japanese Patent Application No. 2010-004324.

  A 100 mL round bottom flask was charged with compound (7 ′) (973 mg, 2.0 mmol), compound 8 (466 mg, 1 mmol), DMF (10 mL), bubbled with argon gas for 30 minutes, and then tris (dibenzylideneacetone). Di-palladium (0) (18.3 mg, 0.02 mmol) and tri (ortho-tolyl) 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 layers were 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. By purifying this with column chromatography (fixed layer: (neutral silica gel (manufactured by Kanto Chemical) + 10 wt% potassium fluoride, solvent: hexane / ethyl acetate, 9/1 → 8/2, v / v), A yellow solid was obtained, which was recrystallized from hexane / ethanol to obtain a compound (Comparative 1) as a yellow solid (yield 680 mg, yield 79.3%).

The analysis results of the compound (Comparative 1) 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)
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)
Melting point: 113.7-114.7 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Comparative 1).

  Next, using the specific compound intermediate synthesized in the above synthesis example, the π-electron conjugated compound precursor used in the present invention was synthesized.

Next, using the specific compound intermediate synthesized in the above synthesis example, the π-electron conjugated compound precursor used in the present invention was synthesized.
<Synthesis of Compound (Act 1)>
A compound (Ex. 1) was synthesized according to the following reaction formula (scheme).

In a 100 mL round bottom flask, put compound (7-1) (550 mg, 1.49 mmol), compound (8) (346 mg, 0.74 mmol), N, N-dimethylformamide (hereinafter abbreviated as DMF, approximately 10 mL), After bubbling with argon gas for 30 minutes, tris (dibenzylideneacetone) dipalladium (0) (18.3 mg, 0.02 mmol), tri (ortho-tolyl) phosphine (24.4 mg, 0.08 mmol) were added, and an argon atmosphere was added. Stir at room temperature for 24 hours. The reaction solution was diluted with dichloromethane, water was added, and the organic layer was separated. The water bath was extracted three times with dichloromethane, and the combined organic layers were washed with a saturated aqueous potassium fluoride solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was passed through a silica gel pad (thickness 3 cm) and then concentrated to obtain a red solid. This was washed with methanol and hexane to obtain a yellowish green solid (yield 235 mg).
Separation and purification by recycle preparative HPLC (manufactured by Nihon Analytical Industrial Co., Ltd., LC-9104) gave compounds (Act 1) and Compound (Act 2) as yellow crystals [Compound (Act 1): Yield 85 mg. Compound (Ac. 2): Yield 110 mg].

The analysis results of the compound (Ex. 1) are shown below.
[Compound (Act 1)];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 6H, J = 6.9 Hz), 1.21-1.31 (m, 8H), 1.57-1. 63 (m, 4H), 2.27 (td, 2H, J 1 = 7.6 Hz J 2 = 1.7 Hz), 2.60-2.70 (m, 4H), 5.95 (t, 1H, J = 5.2 Hz), 6.03-6.09 (m, 4H), 6.63 (d, 2H, J = 9.7 Hz), 7.40 (d, 4H, J = 8 .1 Hz), 7.49 (s, 2H), 7.491 (dd, 2H, J ₁ = 7.7 Hz, J ₂ = 2.3 Hz)
Accurate mass (LC-TofMS) (m / z): 624.232 (actual value), 624.237 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structures of the compound (Act 1) and the compound (Act 2).

<Synthesis of Compound (Act 2)>
According to the above reaction formula (scheme), the compound (Act 1) was synthesized together with the compound (Act 1) by the synthesis method of the compound (Act 1). -9104) to obtain the compound (Act 2) as yellow crystals (Act 2): Yield 110 mg].

The analysis results of the compound (Ex. 2) are shown below.
[Compound (Act 2)];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.5 Hz), 1.22-1.32 (m, 4H), 1.57-1. 64 (m, 2H), 2.28 (td, 2H, J 1 = 7.7 Hz J 2 = 1.2 Hz), 2.62-2.72 (m, 2H), 6.03-6. 10 (m, 2H), 6.63 (d, 1H, J = 9.8 Hz), 7.40-7.42 (m, 2H,), 7.46-7.52 (m, 3H), 7.53 (s, 1H), 7.61 (s, 1H), 7.79 (dd, 2H, J 1 = 8.6 Hz J 2 = 1.7 Hz), 7.84 (d, 1H, J = 8.1 Hz), 7.88 (d, 2H, J = 8.1 Hz), 8.07 (d, 1H, J = 8.1 Hz),
Accurate mass (LC-TofMS) (m / z): 508.149 (actual value), 508.153 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 2).

<Synthesis of Compound (Act 3)>
A compound (Act 3) was synthesized according to the following reaction formula (scheme).

  The reaction was conducted in the same manner as in Example 2 except that the compound (7-1) was replaced with the compound (7-2), and the compound (Act 3) was obtained as a yellow crystal by purification. (Yield 253 mg, 75% yield).

The analysis results of the compound (Act 3) are shown below.
[Compound (Act 3)];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.60-2.70 (m, 4H), 3.38 (s, 6H), 5.90 (t, 2H, J = 5.2) Hz), 6.03-6.09 (m, 4H), 6.63 (d, 2H, J = 9.7 Hz), 7.40 (d, 4H, J = 8.1 Hz), 7. 49 (s, 2H), 7.50 (dd, 2H, J 1 = 7.7Hz, J 2 = 2.3 Hz)
Accurate mass (LC-TofMS) (m / z): 456.127 (actual measured value), 456.122 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 3).

<Synthesis of Compound (Act 4)>
Compound (Act 4) was synthesized according to the following reaction formula (scheme).

The reaction was conducted in the same manner as in Example 2 except that the compound (7-1) was replaced with the compound (7-3), and purification was carried out to obtain a compound (Act 4) as yellow crystals. (Yield 291 mg, 60% yield).
The analysis results of the compound (Ex. 4) are shown below.

[Compound (Act 4)];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 6H, J = 6.9 Hz), 1.21-1.31 (m, 8H), 1.57-1. 63 (m, 4H), 2.60-2.70 (m, 4H), 4.15-4.17 (m, 2H), 5.95 (t, 2H, J = 5.2 Hz), 6 .03-6.09 (m, 4H), 6.63 (d, 2H, J = 9.7 Hz), 7.40 (d, 4H, J = 8.1 Hz), 7.49 (s, _{2H), 7.491 (dd, 2H} , J 1 = 7.7Hz, J 2 = 2.3 Hz)
Accurate mass (LC-TofMS) (m / z): 656.232 (actual value) 656.227 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 4).

<Synthesis of Compound (Real 5)>
Compound (Act 5) was synthesized according to the following reaction formula (scheme).

The reaction was conducted in the same manner as in Example 2 except that the compound (7-1) was replaced with the compound (7-4), and purification was performed to obtain the compound (Actu 5) as yellow crystals. (Yield 193 mg, Yield 45.5%).
(Here, in the above formula, TMS group is an abbreviation for trimethylsilyl group.)

The analysis results of the compound (Act 5) are shown below.
[Compound (Actual 5)];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.04 (s, 18H), 2.60-2.70 (m, 4H), 5.15 (t, 2H, J = 5.2) Hz), 6.00 (t, 2H, J = 5.2 Hz), 6.03-6.09 (m, 4H), 6.63 (d, 2H, J = 9.7 Hz), 7. 40 (d, 4H, J = 8.1 Hz), 7.48 (s, 2H), 7.50 (dd, 2H, J 1 = 7.7Hz, J 2 = 2.3 Hz)
Accurate mass (LC-TofMS) (m / z): 572.175 (actual measured value), 572.170 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 5).

[Synthesis of Compound (Act 6)]
Compound (Act 6) was synthesized according to the following reaction formula (scheme).

[Synthesis of Compound (Act 6-1)]
In a 200 mL three-necked flask, compound 9 (2.58 g, 5 mmol), compound 10 (2.2 eq, 11 mmol, 2.52 g) and toluene (100 mL) were taken, and after bubbling with argon gas for 30 minutes, Tris (dibenzylideneacetone) dipalladium (0) (229 mg, 0.25 mmol) and tri (orthotolyl) phosphine (304 mg, 1.0 mmol) were added, and the mixture was refluxed for 8 hours under an argon atmosphere.
The reaction solution was filtered through a silica gel pad (thickness 3 cm), and the filtrate was concentrated to obtain a brown solid. By recrystallizing this from toluene, a compound (Ex. 6-1) was obtained as pale yellow crystals.
(Yield 1.85 g, Yield 76%)

The analysis results of the compound (Ex. 6-1) are shown below.
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 the compound (Ex. 6-1).

[Synthesis of Compound (Ex. 6-2)]
A 300 mL round bottom flask was charged with compound (real 6-1) (1.8 g, 3.7 mmol), water (30 mL), methanol (30 mL), THF (90 mL), and replaced with argon gas. Lithium monohydrate (3 eq, 11.1 mmol, 466 mg) was added, and the mixture was stirred at 80 ° C. for 3 hr. After cooling to room temperature, the system is acidified by adding concentrated hydrochloric acid, and the deposited precipitate is filtered through a PTFE filter, washed with water and then with hexane, dried at 60 ° C. under reduced pressure, and pale yellow Compound (Ex. 6-2) was obtained as a solid. (Yield 1.6g, 94%)

The analysis results of the compound (Ex. 6-2) are shown below.
Mass spectrometry: GC-MS m / z = 458 (M +)
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 3.79 (s, 4H), 7.39-7.44 (m, 6H), 7.47 (s, 2H), 7.53 ( _{dd, 2H, J 1 = 6.9} Hz, J 2 = 1.7 Hz), 8.49 (s, 2H), 12.3-12.5 (br, 2H)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 6-2).

[Synthesis of Compound (Ex. 6-3)]
In a 100 mL round bottom flask, the compound (ex. 6-2) (2 mmol, 916 mg) was taken and replaced with argon gas, and then trifluoromethanesulfonic anhydride (10 mL), diphosphorus pentaoxide (0 mL) under ice cooling. 0.5 g) was added and stirred at that temperature for 2 hours. The contents were poured into ice water (200 g), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain the compound (Ex. 6-3) as a yellow solid. Used in the next reaction without further purification.

The analysis results of the compound (Ex. 6-3) are shown below.
Mass spectrometry: GC-MS m / z = 422 (M +)
IR: 1720 (C = O, ketone)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 6-3).

[Synthesis of Compound (Act 6)]
In a 100 mL round bottom flask, take compound (Ex. 6-3) (2 mmol, 844 mg), add methanol (20 mL), THF (40 mL), and add sodium borohydride (5 eq, 10 mmol, 378 mg) under ice cooling. In addition, the mixture was stirred at the same temperature for 2 hours. The contents were poured into ice water (200 g), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain a pale yellow solid. It was used for the next reaction after drying under reduced pressure without further purification.
In a separate 100 mL round bottom flask, the above solid, DMAP (0.1 mmol, 12.2 mg) was taken and replaced with argon gas. After adding THF (20 mL) and pyridine (2 mL), caproic acid chloride ( 4 eq, 8 mmol, 1.07 g) was added dropwise over 5 minutes, and the mixture was stirred for 4 hours at the same temperature until the raw material disappeared. Water (100 mL) and ethyl acetate (100 mL) were added to the reaction solution, and the organic layer was separated. The aqueous layer was extracted twice with ethyl acetate (30 mL), and the combined organic layer was washed with saturated brine and dried over sodium sulfate. The filtrate was concentrated to obtain a crude product of the compound (Act 6) as a yellow solid. This was produced by column chromatography (stationary phase: silica gel, mobile phase: toluene) to obtain a pale yellow solid. Further, recrystallization from toluene / ethanol gave the compound (Act 6) as pale yellow crystals. (Yield 149 mg, Yield 12%)

The analysis results of the compound (Act 6) are shown below.
Accurate mass (LC-TofMS) (m / z): 622.228 (actual value), 622.221 (calculated value)
Mass spectrometry: GC-MS m / z = 622 (M +), 390 (thermal decomposition product)
Decomposition temperature: 200 degrees or less From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Act 6).

[Synthesis of Compound (Act 7)]
Compound (Act 7) was synthesized according to the following reaction formula (scheme).

[Synthesis of Compound (Act 7-1)]
In a 200 mL three-necked flask, compound 10 (2.0 g, 8.7 mmol), compound 11 (3.92 mmol, 1.78 g), potassium phosphate hydrate (13 g), DMF / toluene (1/1, 100 mL) and bubbling with argon gas for 30 minutes, then added tris (dibenzylideneacetone) dipalladium (0) (383 mg, 0.42 mmol), tri (orthotolyl) phosphine (510 mg, 1.67 mmol), The mixture was stirred at 85 ° C. for 7 hours under an argon atmosphere. A saturated ammonium chloride solution, water and toluene were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted twice with toluene. The combined organic layers were washed with water followed by saturated brine and dried over magnesium sulfate. The filtrate was concentrated to give a yellow solid.
This was subjected to column purification (stationary phase: silica gel, mobile phase: toluene → toluene / ethyl acetate = 9/1) to obtain the compound (ex. 7-1) as a yellow solid.
(Yield 1.09 g, 56% yield)

The analysis results of the compound (Ex. 7-1) are shown below.
Mass spectrometry: GC-MS m / z = 498 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 7-1).

[Synthesis of Compound (Act 7-2)]
A 300 mL round bottom flask was charged with compound (real 7-1) (498 mg, 1 mmol), water (5 mL), methanol (5 mL), THF (15 mL), purged with argon gas, and then lithium hydroxide monohydrate. The product (3 eq, 140 mg) was added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, 1N hydrochloric acid was added to acidify the system, and ethyl acetate was added to separate the organic layer. The aqueous layer was repeatedly extracted twice with ethyl acetate and the combined organic layers were washed with water followed by saturated brine and dried over sodium sulfate. The filtrate was concentrated to give compound real 7-2 as a yellow solid. (Yield 447 mg, Yield 95%)

The analysis results of the compound (Ex. 7-2) are shown below.
Mass spectrometry: GC-MS m / z = 470 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 7-2).

[Synthesis of Compound (Act 7-3)]
In a 100 mL round bottom flask, the compound (7-2) (0.8 mmol, 376 mg) was taken and replaced with argon gas, and then trifluoromethanesulfonic anhydride (10 mL), diphosphorus pentaoxide (0 0.5 g) was added and stirred at that temperature for 2 hours. The contents were poured into ice water (200 g), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain the compound (ex. 7-3) as a yellow solid. Used in the next reaction without further purification.

The analysis results of the compound (Ex. 7-3) are shown below.
Mass spectrometry: GC-MS m / z = 434 (M +)
IR: 1724 (C = O, ketone)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 7-3).

[Synthesis of Compound (Act 7)]
In a 100 mL round-bottom flask, take compound (Ex. 7-3) (0.8 mmol, 376 mg), add methanol (20 mL) and THF (40 mL), and add sodium borohydride (5 eq, 4.0 mmol) under ice cooling. 151 mg), and the mixture was stirred at the same temperature for 2 hours.
The contents were poured into ice water (200 g), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain a pale yellow solid. It was used for the next reaction after drying under reduced pressure without further purification.
In a separate 100 mL round bottom flask, the above solid, DMAP (0.1 mmol, 12.2 mg) was taken and replaced with argon gas, and then THF (20 mL) and pyridine (2 mL) were added. Noyl chloride (4 eq, 3.2 mmol, 517 mg) was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 6 hours until the raw material disappeared. Water (100 mL) and ethyl acetate (100 mL) were added to the reaction solution, and the organic layer was separated. The aqueous layer was extracted twice with ethyl acetate (30 mL), and the combined organic layer was washed with saturated brine and dried over sodium sulfate. The filtrate was concentrated to obtain a crude product of the compound (Act 7) as a yellow solid. This was purified by column chromatography (stationary phase: silica gel, mobile phase: toluene → toluene / ethyl acetate = 95/5) to obtain a pale yellow solid. Further, recrystallization from toluene / ethanol gave the compound (Act 7) as a pale yellow solid. (Yield 57.5 mg, Yield 10%)

The analysis results of the compound (Act 7) are shown below.
Accurate mass (LC-TofMS) (m / z): 718.408 (actual value), 718.402 (calculated value)
Mass spectrometry: GC-MS m / z = 718 (M +), 402 (thermal decomposition product)
Decomposition temperature: 200 degrees or less From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 7).

[Synthesis of Compound (Act 8)]
A compound (Act 8) was synthesized according to the following reaction formula (scheme).

[Synthesis of Compound (Act 8-1)]
Compound 13 (1.6 g, 3.6 mmol), potassium carbonate saturated aqueous solution 20 mL, and THF 40 mL were added to a 200 mL three-necked flask, and argon bubbling was performed for 30 minutes. Thereafter, 2-naphthaleneboronic acid (1.55 g, 9.0 mmol) and tetrakis (triphenylphosphine) palladium (0) 208 mg, 0.36 mM) were added, and the mixture was heated and stirred at 75 ° C. for 8 hours. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature and the precipitated target product was filtered off. Recrystallization with toluene gave the target product of Ex. Yield 800 mg, Yield 50%

The analysis results of the compound (Ex. 8-1) are shown below.
Mass spectrometry: GC-MS m / z = 446 (M +)
From the above analysis results and the Rf value of TLC, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 8-1).

  In a 100 mL round bottom flask, the compound (Ex. 8-1) (821 mg, 2 mmol) was taken and replaced with argon gas, and then trifluoromethanesulfonic anhydride (10 mL), diphosphorus pentaoxide (0 0.5 g) was added and stirred at that temperature for 2 hours. The contents were poured into ice water (200 g), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain the compound (Act 8-2) as a yellow solid. In addition to the compound (Ex. 8-2), an enol which is a tautomer was also observed, but it was used in the next reaction without further purification.

The analysis results of the compound (Ex. 8-2) are shown below.
Mass spectrometry: GC-MS m / z = 410 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 8-2).

[Synthesis of Compound (Act 8)]
In a 100 mL round-bottom flask, take compound (Ex. 8-2) (1 mmol, 410 mg), add ethanol (20 mL) and THF (40 mL), and add sodium borohydride (5 eq, 5 mmol, 189 mg) under ice cooling. In addition, the mixture was stirred at the same temperature for 2 hours. The contents were poured into ice water (200 g), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain a pale yellow solid. It was used for the next reaction after drying under reduced pressure without further purification.
In a separate 100 mL round bottom flask, the above solid and DMAP (0.1 mmol, 12.2 mg) were taken and replaced with argon gas. Then, THF (50 mL) and pyridine (2 mL) were added, and pivaloyl chloride was added under ice cooling. (4 eq, 8 mmol, 1.07 g) was added dropwise over 5 minutes, and the mixture was stirred for 4 hours at the same temperature until the raw material disappeared. Water (100 mL) and ethyl acetate (100 mL) were added to the reaction solution, and the organic layer was separated. The aqueous layer was extracted twice with ethyl acetate (30 mL), and the combined organic layer was washed with saturated brine and dried over sodium sulfate. The filtrate was concentrated to obtain a crude product of the compound (Ex. 8) as a yellow solid. This was purified by column chromatography (stationary phase: silica gel, mobile phase: toluene) to obtain a pale yellow solid. Further, recrystallization from toluene / ethanol gave the compound (Ex. 8) as pale yellow crystals. (Yield 87 mg, Yield 15%)

The analysis results of the compound (Ex. 8) are shown below.
Accurate mass (LC-TofMS) (m / z): 582.273 (actual value), 582.2277 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the compound (Ex. 8).

[Synthesis of Compound (Act 9)]
Compound (Act 9) was synthesized according to the following reaction formula (scheme).

[Synthesis of Compound (Act 9-1)]
Compound 13 (1.6 g, 1.0 mmol), potassium phosphate 0.5 g, and DMF 30 mL were added to a 200 mL three-necked flask, and argon bubbling was performed for 30 minutes. Thereafter, 1-pyrenylboronic acid (0.62 g, 2.5 mmol) and tetrakis (triphenylphosphine) palladium (0) (104 mg, 0.18 mM) were added, and the mixture was heated and stirred at 70 degrees for 8 hours. After cooling to room temperature, the precipitated target product was filtered off. By washing with hexane and recrystallizing with toluene, the target product of Example 9-1 was obtained. Yield 500 mg, yield 84.1%.
The analysis results of the compound (Ex. 8-1) are shown below.
Mass spectrometry: GC-MS m / z = 594 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 9-1).

[Synthesis of Compound (Act 9-2)]
In a 100 mL round-bottom flask, the compound (Ex. 9-1) (1.49 g, 2.5 mmol) was taken and replaced with argon gas, and then trifluoromethanesulfonic anhydride (50 mL), pentoxide was cooled with ice. Diphosphorus (1 g) was added and stirred at that temperature for 8 hours. The contents were poured into ice water (1 kg in total), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain the compound (Act 9-2) as a yellow solid. In addition to the compound (Ex. 9-2), an enol form which is a tautomer was also seen, but it was used in the next reaction without further purification.

The analysis results of the compound (Ex. 9-2) are shown below.
Mass spectrometry: GC-MS m / z = 558 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 9-2).

[Synthesis of Compound (Act 9)]
In a 300 mL round bottom flask, the compound (real 9-2) (1.3 mmol, 726 mg) is taken, ethanol (50 mL) and THF (200 mL) are added, and sodium borohydride (7.8 mmol, 295 mg) is cooled with ice. ) And stirred at the same temperature for 2.5 hours.
The contents were poured into ice water (1 Kg), and the deposited precipitate was collected by filtration and washed with water and then with hexane to obtain a pale yellow solid. It was used for the next reaction after drying under reduced pressure without further purification.
In a separate 300 mL round-bottom flask, the above solid and DMAP (0.13 mmol, 15.9 mg) were taken and replaced with argon gas, and then THF (200 mL) and pyridine (10 mL) were added. Noyl chloride (1.13 g, 5.2 mmol) was added dropwise as it was, and the mixture was stirred for 4 hours until the raw material disappeared at 0 degrees. After returning to room temperature, water (100 mL) and ethyl acetate (100 mL) were added to the reaction solution, and the organic layer was separated. The aqueous layer was extracted twice with ethyl acetate (30 mL), and the combined organic layer was washed with saturated brine and dried over sodium sulfate. The filtrate was concentrated to obtain a crude product of the compound (Real 9) as a yellow solid. This was purified by column chromatography (stationary phase: silica gel, mobile phase: toluene) to obtain a pale yellow solid. (Yield 84 mg, Yield 7%)

The analysis results of the compound (Act 9) are shown below.
Accurate mass (LC-TofMS) (m / z): 926.533 measured value), 926.527 (calculated value.)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Act 9).

[Synthesis of Compound (Act 10)]
Compound (Act 10) was synthesized according to the following reaction formula (scheme).

[Synthesis of Real 10-1]
In a 100 ml four-necked flask, DMF (30 ml), compound (17) (0.20 g, 0.89 mmol), compound (7-1) (2.2 eq, g, 1.96 mmol, 726 mg), triphenylphosphine ( 9.1 mg, 0.034 mol) and triethylamine (0.34 mL, 2.4 mmol) were added. The mixture was stirred for 45 minutes while bubbling with argon gas. Palladium acetate (3.9 mg, 0.017 mmol) was added and stirred at 50 degrees for 24 hours.
The mixture was cooled to room temperature, filtered through celite, and the resulting solution was extracted with chloroform. The organic layer was washed with water saturated brine, and then the organic layer was dried over magnesium sulfate. Magnesium sulfate is filtered off and the solid obtained by concentration is dissolved in a minimum amount of toluene, and the concentrated solid is regenerated through a silica gel pad (thickness 2 cm) by recycle GPC (manufactured by Nihon Analytical Industries, Ltd.) The product (Ex. 9-1) was obtained as a yellow solid. (Yield 444 mg, Yield 70%)

The analysis results of the compound (Ex. 10-1) are shown below.
Accurate mass (LC-TofMS) (m / z): 714.378 (actual measured value), 714.372 (calculated value.)
Mass spectrometry: GC-MS m / z = 714 (M +), 483 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 10-1).

[Synthesis of Compound (Act 10)]
Cyclohexane (300 ml), compound (real 10-1) (130 mg, 0.182 mmol) and iodine (30 mg, 0.117 mmol) were placed in a 500 ml four-necked flask. A low-pressure mercury lamp (manufactured by Ushio) was irradiated for 5 hours. After cyclohexane was distilled off under reduced pressure, water and chloroform were added to the residue, the organic layer was separated, and the aqueous layer was extracted twice with chloroform. The combined organic layers were washed with aqueous sodium thiosulfate solution, water and saturated brine, and then dried over sodium sulfate. The filtrate was concentrated to give a yellow oily solid. This was separated from by-products and purified by recycled GPC (manufactured by Nihon Analytical Industrial Co., Ltd.) to obtain a compound (Act 10) as a pale yellow solid. (Yield 28.6 mg, Yield 22%)

The analysis results of the compound (Ex. 10) are shown below.
Accurate mass (LC-TofMS) (m / z): 714.336 (actual value), 714.340 (calculated value)
Mass spectrometry: GC-MS m / z = 714 (M +), 479 (thermal decomposition product)
Decomposition temperature: 200 ° C. or less From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 10).

[Synthesis of Compound (Act 11)]
Compound (Ex. 11) was synthesized according to the following reaction formula (scheme).

Compound (24) (275 mg, 0.785 mmol), compound (7-5) (750 mg, 1.65 mmol), copper iodide (20.0 mg) were placed in a 100 mL round bottom flask, and THF (30 mL), diisopropylethylamine was added. (1.5 mL) was added and replaced with argon gas, and then PdCl ₂ (PPh ₃ ) ₂ (16.6 mg) was added and stirred at room temperature for 72 hours.
Dichloromethane (100 mL) and water (100 mL) were added to separate the organic layer, and the aqueous layer was extracted twice with dichloromethane. The combined organic layers were washed with water and then with saturated brine and dried over sodium sulfate. The filtrate was concentrated and dissolved in a minimum amount of dichloromethane and the solution was passed through an alumina pad (activity II (water content 3%)) and concentrated again to give a yellow oil. This was purified by recycled GPC (manufactured by Nihon Analytical Industrial Co., Ltd.) to obtain a compound (Act 11) as a yellow solid. (Yield 273 mg, Yield 34.7%)

The analysis results of the compound (Ex. 11) are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.74-0.83 (m, 12H), 1.10-1.32 (m, 24H), 1.36-1.43 (m , 4H), 1.50-1.60 (m, 4H), 2.2-2.32 (m, 2H), 2.56-2.62 (m, 2H), 2.65-2.71 (M, 2H), 6.03-6.08 (m, 4H), 6.56 (d, 2H, J = 9.0 Hz), 7.33 (s, 2H), 7.36-7. 41 (m, 4H), 7.48 (s, 2H), 8.28 (s, 2H)
Accurate mass (LC-TofMS) (m / z): 714.336 (actual value), 714.340 (calculated value)
Mass spectrometry: GC-MS m / z = 1003 (M +), 603 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 11).

[Synthesis of Compound (Real 12)]
12 A compound (Ex. 12) was synthesized according to the following reaction formula (scheme).

Compound (23) (546 mg, 1.0 mmol), ethynylbenzene (224 mg, 2.2 mmol) and copper iodide (30.0 mg) were placed in a 100 mL round bottom flask, and THF (30 mL) and diisopropylethylamine (2. 5 mL) was added, and the atmosphere was replaced with argon gas. Then, PdCl ₂ (PPh ₃ ) ₂ (32.0 mg) was added, and the mixture was stirred at room temperature for 72 hours. Dichloromethane (100 mL) and water (100 mL) were added to separate the organic layer, and the aqueous layer was extracted twice with dichloromethane. The combined organic layers were washed with water and then with saturated brine and dried over sodium sulfate. The filtrate was concentrated and dissolved in a minimum amount of dichloromethane and the solution was passed through an alumina pad (activity II (water content 3%)) and concentrated again to give a yellow oil. This was purified by recycled GPC (manufactured by Nihon Analytical Industrial Co., Ltd.) to obtain a compound (Act 12) as a pale yellow solid. (Yield 292 mg, Yield 59.0%)

The analysis results of the compound (Ex. 12) are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.2 Hz), 1.21-1.30 (m, 4H), 1.54-1. 60 (m, 2H), 2.20-2.23 (m, 2H), 3.05 (d, 2H), 6.05 (t, 1H), 7.2-7.95 (m, 16H)
Mass spectrometry: GC-MS m / z = 495 (M +), 378 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the compound (Ex. 12).

<Example of conversion by substitution group elimination>
Next, a conversion example of the π-electron conjugated compound precursor synthesized in the above example to a π-electron conjugated compound (specific compound) by elimination of substituents is shown.

[Conversion of π-Electron Conjugated Compound Precursor Compound (7) to 2-iodonaphthalene by Substituent Elimination]

<Synthesis of 2-iodonaphthalene>
2-Iodonaphthalene was synthesized according to the following reaction formula (scheme).

  The compound (7-1) (100 mg) synthesized in <Synthesis of Compound (7-1)> in Synthesis Example 1 was placed in a round bottom flask, and the flask was stirred for 1 hour while maintaining the internal temperature at 140 ° C. The flask was vacuum-dried at 50 ° C. for 1 hour, and then colorless crystals remaining in the flask were scraped off (yield 68.5 mg, yield 99.8%).

The analysis results of this crystal are shown below.
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 _{(C 10 H 7 I):} C, 47.11; H, 2.94 ( Found), C, 47.27; H, 2.78 ( theoretical value)
Mass spectrometry: GC-MS m / z = 254 (M +)
Melting point: 50.5-52.0 ° C
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were 2-iodonaphthalene.

[Comparative Example 1]
[Trial of conversion to 2-iodonaphthalene when π-electron conjugated compound precursor compound (7 ′) is used]
Conversion to 2-iodonaphthalene by elimination of a substituent in the same manner as in Example 13 except that the compound (7-1) used in Example 13 was changed to the compound (7 ′) used in Synthesis Example 3. Tried.
When the pale yellow liquid remaining in the flask was analyzed, it was confirmed that conversion to 2-iodonaphthalene by elimination of the substituent was not performed and the compound (7 ′) remained as it was.

<Example of conversion by substitution group elimination>
[Conversion of a π-electron conjugated compound precursor compound (Ex. 1) into a compound (24) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (24)]>
Compound (24) was synthesized according to the following reaction formula (scheme).

  The compound synthesized in Example 1 (Real 1) (50 mg, 0.159 mmol) was placed in a round bottom flask, and heated and stirred at 140 ° C. (flask temperature) for 1 hour under an argon atmosphere. A bright yellow solid was obtained. This was washed with toluene, followed by methanol, and dried under vacuum to obtain compound (24) as yellow crystals (yield 30.2 mg, yield 96.1%).

The analysis result of the compound (24) is shown below.
Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.54; H, 4.00; S, 16.20 (actual value) C, 79.55; H, 4.11; S, 16.34 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 392.068 (actual value), 392.069 (calculated value)
Melting point: 357.7 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (24).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (act 2) to the compound (24) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (24)]>
In Example 14, the reaction was carried out in the same manner as in Example 14 except that the heating temperature was changed from 140 ° C. to 130 ° C. using the compound (real 2) instead of the compound (real 1) to obtain the desired product. (Yield 97.0%)
The analysis results of the obtained yellow crystals are shown below.

Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.50; H, 4.01; S, 16.23 (actual value), C, 79.55; H, 4.11; S, 16. 34 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 392.066 (actual value), 392.069 (calculated value)
Melting point: 357.9 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (24).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (act 3) to the compound (24) by elimination of substituents]
In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 180 ° C. and the heating time was changed from 1 hour to 4 hours using the compound (real 3) instead of the compound (real 1). To obtain the target product. (Yield 95.5%)
The analysis results of the obtained yellow crystals are shown below.

Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.50; H, 4.05; S, 16.24 (actual value), C, 79.55; H, 4.11; S, 16. 34 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 392.072 (actual value), 392.069 (calculated value)
Melting point: 358.3 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (24).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (act 4) to the compound (24) by elimination of substituents]
In Example 14, instead of the compound (Ex. 1), the reaction was carried out in the same manner using the compound (Ex. 4) to obtain the desired product. (Yield 97.3%)
The analysis results of the obtained yellow crystals are shown below.

Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.51; H, 4.04; S, 16.30 (actual value), C, 79.55; H, 4.11; S, 16. 34 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 392.075 (actual measured value), 392.069 (calculated value)
Melting point: 358.0 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (24).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (act 5) to the compound (24) by elimination of substituents]
In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 180 ° C. and the heating time was changed from 1 hour to 4 hours using the compound (real 5) instead of the compound (real 1). The target product was obtained. (Yield 95.0%)
The analysis results of the obtained yellow crystals are shown below.

Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.51; H, 4.05; S, 16.28 (actual value), C, 79.55; H, 4.11; S, 16. 34 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 392.073 (actual value), 392.069 (calculated value)
Melting point: 357.9 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (24).

[Comparative Example 2]
<Example of conversion by substitution group elimination>
[Trial of conversion of compound precursor compound (Comparative 1) to compound (24) by elimination of substituents]
In Example 14, the reaction was carried out in the same manner using the compound (Comparative 1) in place of the compound (Act 1). As a result, a light yellow solid was obtained instead of a yellow crystal. When the obtained solid was washed with toluene and subsequently with methanol, the solid was completely dissolved, and the target crystals were not obtained. When this solution was concentrated and the obtained solid was analyzed, the value was confirmed to be an unconverted compound (Comparative 1).

Examples 13 to 18 and Comparative Examples 1 and 2 can be summarized as follows.
According to the π-electron conjugated compound precursor of the present invention, approximately 95% or more by heating (energy application: external stimulation) at a lower temperature (in comparison with the same skeleton) than the conventional π-electron conjugated compound precursor. It was shown that it is possible to obtain a high yield and low solubility organic semiconductor compound with high yield and high purity. As a result, it was suggested that this is an effective method not only for producing a low molecular weight compound such as naphthalene but also for producing a π-conjugated compound (especially an organic semiconductor compound) that is hardly soluble in nature. This can be applied to organic pigments and many other molecules besides organic semiconductors.

  From Example 11, Comparative Example 1, Example 12, and Comparative Example 2 having the same leaving group and converted skeleton, the skeleton (cyclohexadiene skeleton) unique to the π-electron conjugated compound precursor of the present invention is converted. It was found that it contributed to lowering the temperature. Conventionally, heating conditions of 250 to 300 ° C. or higher have been required for elimination of substituents, and silyl ethers and alkyl ethers other than acyloxy groups are also incorporated into the main skeleton of the present invention at 200 ° C. or lower. Conversion was confirmed.

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (act 6) to the compound (25) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (25)]>
Compound (25) was synthesized according to the following reaction formula (scheme).

  In Example 14, the reaction was performed in the same manner except that the heating temperature was changed from 140 ° C. to 150 ° C. and the heating time was changed from 1 hour to 2 hours using the compound (real 6) instead of the compound (real 1). Went. The analysis results of the obtained orange crystals are shown below.

Elemental analysis (C ₂₆ H ₁₄ S ₂ ): C, 79.50; H, 4.01; S, 16.23 (actual value), C, 79.55; H, 4.11; S, 16. 34 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 390.060 (actual value), 390.054 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (25).

<Example of conversion by substitution group elimination>
[Conversion of π-electron conjugated compound precursor compound (act 7) to compound (26) by substituent elimination)

<Synthesis of Organic Semiconductor Compound [Compound (26)]>
Compound (26) was synthesized according to the following reaction formula (scheme).

In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 150 ° C. and the heating time was changed from 1 hour to 2 hours using the compound (real 7) instead of the compound (real 1). To obtain the target product. (Yield 94.9%)
The analysis results of the obtained crystals are shown below.

Elemental analysis (C ₃₂ H ₁₈ ): C, 95.25; H, 4.71 (actual value), C, 95.49; H, 4.51 (theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 402.149 (actual value), 402.141 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (26).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (actual 8) to the compound (27) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (27)]>
Compound (27) was synthesized according to the following reaction formula (scheme).

In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 150 ° C. and the heating time was changed from 1 hour to 3 hours using the compound (real 8) instead of the compound (real 1). To obtain the target product. (Yield 95.3%)
The analysis results of the obtained crystals are shown below.

Elemental analysis _{(C 30 H 18): C} , 95.11; H, 4.88 ( Found), C, 95.21; H, 4.79 ( theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 378.136 (actual value), 378.141 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (27).

<Example of conversion by substitution group elimination>
[Conversion of π-electron conjugated compound precursor compound (act 9) to compound (28) by substituent elimination)

<Synthesis of Organic Semiconductor Compound [Compound (28)]>
Compound (28) was synthesized according to the following reaction formula (scheme).

In Example 14, the reaction was performed in the same manner except that the heating temperature was changed from 140 ° C. to 150 ° C. and the heating time was changed from 1 hour to 4 hours using the compound (real 9) instead of the compound (real 1). To obtain the target product. (Yield 95.1%)
The analysis results of the obtained crystals are shown below.

Elemental analysis _{(C 42 H 42): C} , 95.59; H, 4.41 ( Found), C, 95.79; H, 4.21 ( theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 526.167 (actual value), 526.172 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (28).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (actual 10) to the compound (29) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (29)]>
Compound (29) was synthesized according to the following reaction formula (scheme).

In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 150 ° C. and the heating time was changed from 1 hour to 2 hours using the compound (real 10) instead of the compound (real 1). To obtain the target product. (Yield 93.3%)
The analysis results of the obtained crystals are shown below.

Elemental analysis value (C ₃₈ H ₂₂ ): C, 95.25; H, 4.71 (actual value), C, 95.37; H, 4.63 (theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 478.165 (actual value), 478.172 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (29).

<Example of conversion by substitution group elimination>
[Conversion of the π-electron conjugated compound precursor compound (Ex. 11) to the compound (30) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (30)]>
Compound (30) was synthesized according to the following reaction formula (scheme).

In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 160 ° C. and the heating time was changed from 1 hour to 4 hours using the compound (real 11) instead of the compound (real 1). To obtain the target product. (Yield 93.3%)
The analysis results of the obtained crystals are shown below.

Elemental analysis (C ₃₈ H ₁₈ S ₄ ): C, 75.79; H, 3.11; S, 21.07 (actual value), C, 75.71; H, 3.01; S, 21. 28 (Theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 602.023 (actual value), 602.029 (calculated value)

From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (30).

<Example of conversion by substitution group elimination>
[Conversion of π-electron conjugated compound precursor compound (Ex. 12) to compound (31) by elimination of substituents]

<Synthesis of Organic Semiconductor Compound [Compound (31)]>
Compound (31) was synthesized according to the following reaction formula (scheme).

In Example 14, the reaction was carried out in the same manner except that the heating temperature was changed from 140 ° C. to 160 ° C. and the heating time was changed from 1 hour to 2 hours using the compound (real 12) instead of the compound (real 1). To obtain the target product. (Yield 95.4%)
The analysis results of the obtained crystals are shown below.

Elemental analysis (C ₃₈ H ₁₈ S ₄ ): C, 95.16; H, 4.60 (actual value), C, 95.21; H, 4.79 (theoretical value)
Accurate mass spectrometry: LC-MS (m / z) = 378.148 (actual value), 378.141 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (31).

<Inkization of organic semiconductor precursor (evaluation of solubility)>
The compounds obtained in Examples 1, 3, 5, 6, 7, 8, 9, 10, 11, 12 and the corresponding specific compounds (24) to (33) were respectively converted to toluene, THF, anisole, chloroform ( 2.0 mg) until the residue remains, stirred for 10 minutes under reflux of the solvent, cooled to room temperature, further stirred for 1 hour, allowed to stand for 16 hours, and the supernatant was filtered with a 0.2 μm PTFE filter. Filtration gave a saturated solution. This was dried under reduced pressure to calculate the solubility of the compound in each solvent. The results are shown in Table 1 below.
The evaluation criteria in Table 1 are as follows.
A: Solubility is 0.5 wt% or more,
○: 0.1 wt% or more and less than 0.5 wt%
Δ: 0.005 wt% or more and less than 0.1 wt%,
X: Less than 0.005 wt%

From the results of Table 1, it can be seen that the π-electron conjugated compound precursor of the present invention has a solubility of about 0.1 wt% or more in a plurality of solvents having different polarities, which is a conventional cyclohexene skeleton. On the other hand, it was clarified that there was no inferiority compared to the case in which two leaving groups were introduced, and that the selectivity of the solvent in the coating process was still high. Since it has such high solubility, various film forming and printing methods such as inkjet coating, spin coating, solution casting, dip coating, screen printing, and gravure printing can be applied.
On the other hand, compound (24) to compound (31), which are the materials after conversion, have a solubility of 0.005 wt% or less in all of these solvents, and the contribution of the soluble group constituting the π-electron conjugated compound precursor is large. I understand that. That is, the compound converted by the elimination reaction is insolubilized. Further, it can be seen that when the molecular size is not so large as in the compound (33), the compound shows solubility even after the elimination of the substituent.

<Observation Example of Desorption Behavior of Compound (Act 1)>
The thermal decomposition behavior of the compound synthesized in Example 1 (Ex. 1) was measured using TG-DTA [reference Al ₂ O ₃ , under a nitrogen stream (200 mL / min), EXSTAR 6000 (trade name), Seiko Instruments Inc. The temperature was raised from 25 ° C. to 500 ° C. at a rate of 5 ° C./min.
In addition, the phase change behavior was determined by DSC [reference Al ₂ O ₃ , under a nitrogen stream (200 mL / min), EXSTAR 6000 (trade name), Seiko Instruments Inc. The temperature was raised from 25 ° C. to 500 ° C. at a rate of 5 ° C./min.
The above results are shown in FIG. In FIG. 4, the horizontal axis represents temperature [° C.], the left vertical axis represents weight change [mg], and the right vertical axis represents heat flow [mW].
In TG-DTA, a weight reduction of 36.4% was observed from 120 ° C to 225 ° C. This is almost in agreement with 2 molecules of caproic acid (theoretical value: 37.1%). The presence of a melting point was observed at 357.4 ° C. This is consistent with the value of compound (24).
From the above results, it was shown that the compound (Ex. 1) was converted to the compound (24) by heating.

<Observation Example of Desorption Behavior of Compound (Act 2)>
The thermal decomposition behavior and phase change behavior were observed in the same manner as in Example 27 except that the compound (Act 1) was changed to the compound (Act 2). The results are shown in FIG. In FIG. 5, the horizontal axis represents temperature [° C.], the left vertical axis represents weight change [mg], and the right vertical axis represents heat flow [mW].
In TG-DTA, a weight loss of 21.9% was observed from 115 ° C to 200 ° C. This is almost identical to one molecule of caproic acid (theoretical value: 22.7%). The presence of a melting point was observed at 357.9 ° C. This is consistent with the value of compound (24).
From the above results, it was shown that the compound (Ex. 2) was converted to the compound (24) by heating.

  In the π-electron conjugated compound precursor (organic semiconductor precursor) of the present invention, elimination of the leaving group occurs in a temperature range lower than 100 ° C. compared to the conventional [for example, compound (Comparative 1)], followed by a molecule. It was found that crystallization of (see DSC exothermic peak) occurred. In addition, it was also found that when the number of soluble groups (leaving substituents) constituting the organic semiconductor precursor is one, the elimination temperature is lowered and the weight reduction completion temperature is low compared to two. .

<Example of thin film production>
The compound (actual 1) and the compound (actual 2) synthesized in Example 1 were each dissolved in THF (5 mg each) to a concentration of 0.1 wt%, and filtered through a 0.2 μm filter. Was prepared. On an N-type silicon substrate having a 300 nm thick thermal oxide film washed for 24 hours in concentrated sulfuric acid, 100 μL of the prepared solution was dropped using a pipette or 5 pL using an inkjet apparatus (manufactured by Ricoh Printing System). The liquid droplets were applied 50 times, covered with a petri dish, and allowed to stand until the solvent was dried to prepare each thin film. Each thin film was subjected to a polarizing microscope and a scanning probe microscope [Contact Mode, Nanopics (trade name), Seiko Instruments Inc. As a result, it was found that a smooth continuous amorphous film was obtained regardless of the thin film formation method. Next, the two thin films were annealed at 150 ° C. for 30 minutes in an argon atmosphere, and the films were 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. The polarization micrographs of these films are shown in FIG. This is because the precursor compound (Act 1) and compound (Act 2) are converted into a compound (24) having a stronger intermolecular interaction in the film by eliminating the ester group which is a soluble group. This is because it became crystalline. Each thin film was insoluble in chloroform, THF, toluene and the like at 25 ° C.

[Comparative Example 3]
Compound (Act 1) and Compound (Act 2) were replaced with Compound (Act 1) and Compound (Act 24) converted from Compound (Act 2), and orthodichlorobenzene heated to 150 ° C. was used instead of THF. A solution was prepared and a thin film was prepared in the same manner as in Example 28 except that. 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 compound that is hardly soluble in some high-boiling solvents and easily precipitates crystals.

[Production and evaluation of organic thin-film transistors by solution process]
A thin film containing the compound (Ex. 1) was produced in the same manner as in Example 28. The thin film was subjected to an annealing treatment at 150 ° C. for 60 minutes in an argon atmosphere to convert it into a thin film (film thickness: 50 nm) made of the compound (24) that is an organic semiconductor.
By using a shadow mask on the thin film, gold is vacuum-deposited (back pressure: 10 ⁻⁴ Pa, deposition rate: 1 to 2 Å / s, film thickness: 50 nm) to form source and drain electrodes (channel length 50 μm, channel width) 2 mm) to form 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 transistor element As a characteristic. FIG. 7 shows an IV characteristic diagram of this FET element.
In FIG. 7, the white circle corresponds to the left side of the vertical axis (the absolute value of the drain current), and the black circle corresponds to the right side of the vertical axis (the square root of the absolute value of the drain current). The horizontal axis is the applied gate voltage.
The field effect mobility was determined from the saturation region in the current-voltage (IV) characteristics of the organic thin film transistor.
In addition, the following numerical formula (1) was used for calculation of the field effect mobility of an organic thin-film transistor.

      Ids = μCinW (Vg−Vth) 2 / 2L (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 channel begins to form. (This is the threshold voltage of the gate.)
Further, the ratio of the on current at the gate voltage of 40V to the off current at 0V was calculated as the on / off ratio. The results are shown in Table 2 below.

  An FET device was prepared in the same manner as in Example 29 except that the compound (Example 1) in Example 29 was replaced with the compound (Example 2) and converted to a thin film made of the compound (24) which is an organic semiconductor. Evaluation was performed. The results are shown in Table 2 below.

[Comparative Example 4]
Using the orthodichlorobenzene solution described in Comparative Example 3, a thin film made of the compound (24), which is an organic semiconductor, was formed on the same substrate as in Example 29, and an FET device was fabricated and evaluated. The results are shown in Table 2 below.

[Comparative Example 5]
Except that the compound (Act 1) was replaced with the compound (Actual comparison) in Example 29, an annealing treatment [for the purpose of conversion to a thin film composed of the compound (24) which is an organic semiconductor] was performed in the same manner as in Example 29. The thin film was formed by applying the above process, and an FET element was fabricated and evaluated for characteristics. The results are shown in Table 2 below.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 6) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 7) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 8) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 9) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 10) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 11) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

  Example 32 was obtained by replacing the compound (Example 1) in Example 29 with the compound (Example 12) to form a thin film and produce a transistor. The transistor using this active layer also showed good p-type transistor characteristics similar to those of Examples 29 and 30.

From the results of the characteristic evaluation shown in Table 2, good FET characteristics cannot be obtained only by dissolving a poorly soluble organic semiconductor compound [compound (24)] in a high boiling point solvent (Comparative Example 4). Also in the method of converting the precursor film, it was found that the conventional [Compound (Comparative 1)] did not obtain good FET characteristics by the treatment at about 150 ° C. (Comparative Example 5).
On the other hand, by using the π-electron conjugated compound precursor of the present invention as an organic semiconductor precursor and converting it to a film containing an organic semiconductor compound, a solution process is used and a relatively low temperature treatment of about 150 ° C. is preferable. It became clear that FET characteristics could be obtained (Examples 29 to 38).

  That is, all of the organic thin film transistors of the present invention exhibit good hole mobility and current on / off ratio, and have excellent characteristics as organic thin film transistors. From this, it was shown that the production method of the present invention is useful also in the production of an organic electronic device element such as an organic thin film transistor.

From the above results, the π-electron conjugated compound precursor of the present invention is excellent in solubility in various organic solvents, and is applied with lower energy (external stimulus such as heating) than the conventional one (eg, compound (Comparative 1)). It is possible to synthesize a specific compound (organic semiconductor compound, etc.) in high yield without producing a terminal olefin by utilizing the elimination reaction that can occur even in the application of Also excellent in process ability.
Moreover, even if it is an organic semiconductor compound that has been difficult to form due to poor solubility, the substituent-elimination compound of the present invention is used as a precursor of the organic semiconductor compound, and after the formation of the film, heat is applied. By applying the production method for converting into the target organic semiconductor compound, a continuous organic semiconductor film can be easily obtained. The organic semiconductor film thus formed can be applied to an organic electronic device, and in particular, an electronic device such as a semiconductor, an optical-electronic device such as an EL light emitting element, electronic paper, various sensors, and RFIDs (radio frequency identification). ) Is expected to be applicable to such fields.

1 Organic semiconductor layer 2 Source electrode 3 Drain electrode 4 Gate electrode 5 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 2009-188386 A JP 2009-215547 A JP 2009-239293 A JP 2009-28394 A JP 2009-84555 A JP 2009-88483 A JP 2006-352143 A JP 2009-275032 A Japanese Patent Application No. 2009-209911

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

Claims (11)

From the coating film formed by applying a coating solution of a solvent containing the π-electron conjugated compound precursor A- (B) m to a substrate, a detachable substituent represented by the following general formula (II) is added. A method for producing a film-like body, characterized in that a film-like body containing a π-electron conjugated compound represented by A- (C) m is produced.

(Here, A is a π-electron conjugated substituent, and B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I). M is a natural number. , B is linked to any atom on Q _{1 to} Q ₆ and any atom on A in the above general formula (I) via a covalent bond, or is fused with any atom on A C has at least a partial structure of the structure represented by the above general formula (Ia).
[In the formulas (I), (Ia) and (II), X and Y represent a hydrogen atom or a detachable substituent, and one of the X and Y is a detachable substituent, and the other is a hydrogen atom. It is. Q _{2 to} Q ₅ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Q ₁ and Q ₆ are a monovalent organic other than a hydrogen atom, a halogen atom or the above-mentioned leaving substituent. It is a group. Q _{1 to} Q ₆ may be bonded to each other between adjacent groups to form a ring. ] The leaving substituent X or Y is an optionally substituted [ether group or acyloxy group] having 1 or more carbon atoms, and one of X and Y may be substituted. The method for producing a film-like body according to claim 1, wherein one or more [ether group or acyloxy group] and the other is a hydrogen atom.   The film-like body according to claim 1 or 2, wherein the coating liquid is applied by a method selected from the group consisting of inkjet coating, spin coating, solution casting, and dip coating. Production method.   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) 4. The production of 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. Method.   The elimination component represented by the general formula (II) desorbed from the compound A- (B) m is either a hydrogen halide, an optionally substituted carboxylic acid, an optionally substituted alcohol, or carbon dioxide. The method for producing a film-like body according to any one of claims 1 to 4, wherein:   6. The compound A- (B) m is solvent-soluble, and the compound A- (C) m produced by elimination of the detachable substituent is solvent-insoluble. The manufacturing method of the film-like body in any one. From the π-electron conjugated compound precursor A- (B) m, the detachable substituent represented by the following general formula (II) is eliminated to produce a π-electron conjugated compound represented by A- (C) m. A method for producing a π-electron conjugated compound characterized by the above.

(Here, A is a π-electron conjugated substituent, and B is a solvent-soluble substituent having at least a partial structure of the structure represented by the general formula (I). M is a natural number. , B is linked to any atom on Q _{1 to} Q ₆ and any atom on A in the above general formula (I) via a covalent bond, or is fused with any atom on A C has at least a partial structure of the structure represented by the above general formula (Ia).
[In the formulas (I), (Ia) and (II), X and Y represent a hydrogen atom or a detachable substituent, and one of the X and Y is a detachable substituent, and the other is a hydrogen atom. It is. Q _{2 to} Q ₅ are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and Q ₁ and Q ₆ are a monovalent organic other than a hydrogen atom, a halogen atom or the above-mentioned leaving substituent. It is a group. Q _{1 to} Q ₆ may be bonded to each other between adjacent groups to form a ring. ]   The leaving substituent X or Y is an optionally substituted [ether group or acyloxy group] having 1 or more carbon atoms, and one of X and Y may be substituted. The method for producing a π-electron conjugated compound according to claim 7, wherein one or more [ether group or acyloxy group] and the other is a hydrogen atom.   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 π-electron conjugated compound according to claim 7, wherein at least one π-electron conjugated compound is selected from the group consisting of compounds linked via a covalent bond. Production method.   10. The compound A- (B) m is solvent-soluble, and the compound A- (C) m produced by elimination of the detachable substituent is solvent-insoluble. The manufacturing method of the pi electron conjugated compound in any one.   The π-electron conjugated compound compound produced by the method according to claim 7.

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