JP5733553B2 - Substituent elimination compound, organic semiconductor material, film thereof and organic transistor using the same - Google Patents

Description

  The present invention relates to a substituent-eliminating compound that is easy to synthesize, has high solubility, and can be eliminated efficiently with application of external energy, an organic semiconductor containing the compound produced using the same, and an organic semiconductor comprising the same And an organic electronic device using the film. The substituent-eliminating compound 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 using a solution process.

In recent years, research and development of organic thin film transistors using organic semiconductor materials has been active.
So far, acene-based materials such as pentacene have been reported as organic semiconductor materials of low-molecular derivatives (see, for example, Patent Document 1 and Non-Patent Document 1).
Organic thin-film transistors using pentacene as an organic semiconductor layer have been reported to have a relatively high mobility, but these acene-based materials have extremely low solubility in general-purpose solvents. When thinning as a layer, it is necessary to go through a vacuum deposition process. Therefore, it does not meet the expectation for an organic semiconductor material that a thin film can be formed by a simple process such as coating and printing as described above.

Furthermore, as one of the acene-based materials similar to pentacene, 2,7-diphenyl [1] benzothieno [3,2- [2] having a structure of the following formula (1) which is a derivative of benzothieno [3,2-b] benzothiophene b] [1] Benzothiophene (refer to Patent Document 2 and Non-Patent Document 2) is deposited on a substrate treated with octadecyltrichlorosilane, whereby mobility comparable to that of pentacene (about 2.0 cm ² / V · s). Degree) and long-term stability in the atmosphere.
However, this does not meet the expectation for an organic semiconductor material that a thin film can be formed by a simple process such as coating or printing, because it needs to undergo a vacuum deposition process like pentacene.

By the way, an organic semiconductor material can be easily formed into a thin film by a simple method using a wet process such as a printing method, a spin coat method, an ink jet method, etc. There is an advantage that the temperature can be lowered.
As a result, it can be formed on plastic substrates with low heat resistance, and display and other electronic devices can be reduced in weight and cost. it can.

Therefore, it has liquid crystallinity, high solvent solubility, can be applied by spin coating, casting, etc., and has a mobility comparable to that of pentacene by heat treatment at a liquid crystal phase temperature (about 100 ° C.) or less. 2,7-dialkyl [1] benzothieno [3,2-b] [1] benzothiophene having the structure of the following formula (2), which is the same derivative showing about 2.0 cm ² / V · s), is applied by a coating method. Has been proposed (see Patent Document 2 and Non-Patent Document 3).
However, in this case, the temperature at which the liquid crystal phase is developed is relatively low at about 100 ° C., and the film structure can be changed by heat treatment even after film formation.

Therefore, in recent years, a low molecular weight compound with high solvent solubility is used as a semiconductor precursor, which is dissolved in a solvent or the like to form a film by a coating process, and then converted into a semiconductor to obtain an organic semiconductor film. A method of manufacturing has been recently reported.
For example, methods for converting to pentacene, porphyrin-based compounds, and phthalocyanine-based compounds using the retro Diels-Alder reaction have been energetically studied. (For example, refer to Patent Documents 3 to 5 and Non-Patent Documents 4 to 7).

As described in Non-Patent Document 4, charge mobility in an organic semiconductor material (charge)
(mobility) depends on the regular molecular arrangement (ordering such as crystallization) of the organic material film, so that the molecular arrangement of the material in the film can be secured by the vapor deposition method. Organic materials having alignment properties are generally poorly soluble in organic solvents. In other words, the semiconductor characteristics of the organic material film and the film forming ease (depending on the coating method) are generally incompatible.
Therefore, in order to make both compatible, it is considered that the precursor in the coating film is converted into an organic semiconductor material after forming the coating film with a coating solution using a semiconductor precursor having a soluble group. If the places disclosed by these documents are deduced to such meaning and interpreted, the contribution of these documents is not low.

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.
In addition, porphyrins and phthalocyanines both require complicated synthesis, so the application range is narrow, and it is necessary to develop substituent compounds that can be synthesized more easily.

In addition, a method has been proposed in which a solvent-soluble precursor having a sulfonate ester-based substituent is externally stimulated to eliminate the substituent and replace it with a hydrogen atom to convert it into phthalocyanine ( (For example, see Patent Document 6)
However, in this method, since the polarity of the sulfonic acid ester is high, the solubility in a nonpolar organic solvent is not sufficient, and the boiling point of the sulfonic acid, which is a desorption component, is high, and it is difficult to remove it outside the system. In addition, there is a problem that the temperature required for conversion from the precursor is relatively high at least 250 ° C. to 300 ° C. or more.

  Further, a method has been proposed in which a nitroester is thermally stimulated to eliminate a substituent and convert it into a naphthalene derivative (see, for example, Non-Patent Document 8). However, nitroesters represented by nitroglycerin, nitrocellulose and the like are unstable and explosive, and thus have a problem in long-term storage stability of the compound.

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 (see, for example, Patent Documents 7 and 8 and Non-Patent Document 7).
In this method, desorption occurs by heating at about 150 ° C. to 250 ° C., but an olefin group (vinyl group, propenyl group, etc.) is generated at the 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.
The present invention has been made in view of the current state of the prior art described above, is easier to synthesize, has better storage stability, has a high solubility in organic solvents, and is highly efficient for the application of external energy. A novel substituent elimination compound capable of group elimination, and by applying external stimuli such as heat to the compound, it can be obtained with high efficiency without generating a chemically unstable terminal olefin group An organic semiconductor material containing a compound, or a film formed using the substituent-eliminating compound of the present invention as an organic semiconductor precursor, and then converted into an organic semiconductor by heat or the like, so that it is hardly soluble even in a solution process An object of the present invention is to provide a continuous film of materials and to provide an organic electronic device (particularly an organic thin film transistor) using the film.

The above-mentioned subject is achieved by the following present invention.
(1) "below following general formula (IV), substituted elimination compound which is a partial structure represented by (V).

（式中、ｎは２以上の整数であり、括弧内の置換基は同一であっても異なっていてもよい。Ａｒは置換基を有していてもよいアリール基またはヘテロアリール基である。ここで、一般式（ＩＶ）および（Ｖ）は、Ａｒがシクロヘキセン誘導体骨格と共有結合を介して結合しているか、縮環していることを表わす。Ｘ _１ ，Ｘ _２ は置換または無置換の炭素数１以上のアシルオキシ基を表し、Ｙ _１ ，Ｙ _２ はともに水素原子であり、Ｘ _１ ，Ｘ _２ は同一でも異なっていてもよく、互いに結合して環状の前記アシルオキシ基を形成していてもよい。Ｒ _１ 乃至Ｒ _４ は水素原子、アルキル基、アリール基、ヘテロアリール基、シアノ基を表す。）」、
（２）「前記Ａｒが
（ｉ）１つ以上の芳香族炭化水素環および芳香族ヘテロ環、若しくは２つ以上の前記環同士が縮環された化合物、
及び
（ii）前記（ｉ）の環同士が共有結合を介して連結された化合物、
からなる群から少なくとも１つ以上選択される化合物であることを特徴とする前記第（１）項に記載の置換脱離化合物」、
（３）「前記芳香族炭化水素環および芳香族ヘテロ環は、ベンゼン環およびチオフェン環であることを特徴とする前記第（２）項に記載の置換基脱離化合物」、
（４）「前記Ａｒがハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルキルオキシ基、炭素数１〜１８のアルキルチオ基およびアリール基からなる群から選択される少なくとも１種の置換基を有していてもよい下記構造式、

(In the formula, n is an integer of 2 or more, and the substituents in parentheses may be the same or different. Ar is an aryl group or heteroaryl group which may have a substituent. Here, the general formulas (IV) and (V) represent that Ar is bonded to the cyclohexene derivative skeleton via a covalent bond or condensed, and X ₁ and X ₂ are substituted or unsubstituted. Represents an acyloxy group having 1 or more carbon atoms, Y ₁ and Y ₂ are both hydrogen atoms, X ₁ and X ₂ may be the same or different, and are bonded to each other to form the cyclic acyloxy group; R _{1 to} R _{4 each} represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a cyano group.
( 2 ) "Ar is (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound in which two or more rings are condensed,
And (ii) a compound in which the rings of (i) are linked via a covalent bond,
The substituted elimination compound according to item ( 1 ), which is a compound selected from the group consisting of:
( 3 ) "Substituent elimination compound according to item ( 2 ), wherein the aromatic hydrocarbon ring and aromatic heterocycle are a benzene ring and a thiophene ring",
( 4 ) "Ar is at least one selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyloxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms and an aryl group. The following structural formula, which may have a substituent:

であることを特徴とする前記第（１）項乃至第（３）項に記載の置換脱離化合物」。

The substituted elimination compound according to any one of ( 1 ) to ( 3 ) above, wherein

According to the present invention, there are provided a substituent-eliminating compound that is easier to synthesize and rich in solubility, and an organic semiconductor material having a structure in which an unstable terminal substituent does not exist due to a substituent-elimination reaction of the substituent-eliminating compound. Is possible.
In addition, an organic semiconductor film is obtained by applying a solution of the substituent-eliminating compound as an organic semiconductor precursor and performing the same elimination reaction, and an organic electronic device using the film, particularly an organic thin film transistor is provided. It is possible.

It is an IR spectrum of Compound 11 (the horizontal axis is the wave number and the vertical axis is the transmittance. From the top, heat treatment was performed at 170 ° C., 180 ° C., 220 ° C., 230 ° C., 240 ° C., 260 ° C. before heating. IR spectra of Compound 11 and Compound 17.) TG-DTA (Compound 11) (Abscissa is temperature [° C.], ordinate is weight change [mg], ordinate is differential heat [mV]) It is a polarizing microscope photograph of the film | membrane of the compound of this invention. It is the schematic of an organic thin-film transistor. It is a current-voltage characteristic diagram of the organic thin film transistor of the present invention.

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

[1. Substituent elimination compound and compound obtained by elimination reaction]
The substituent-eliminating compound of the present invention is characterized by having a specific solvent-soluble substituent, and producing the target compound by applying an external stimulus to the compound to eliminate the specific substituent. Is possible.
The specific solvent-soluble substituent is a halogen atom represented by the following general formulas (I), (III), or (IV) or an acyloxy-substituted cyclohexene structure. By applying an external stimulus to the solvent, the solvent-soluble substituent is converted into a specific leaving substituent (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) represented by the general formulas (IIa) and (IIb). Is converted into a structure represented by the general formula (Ia), (IIIa), or (IVa) in which the cyclohexene structural site is replaced with a benzene ring, and a compound corresponding to the structure is obtained.

(In the above general formula, at least one pair of (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) is both a hydrogen atom, and the remaining pairs are both halogen atoms, substituted or non-substituted with 1 or more carbon atoms. A substituted acyloxy group having 1 or more carbon atoms, and a pair of acyloxy groups of (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) may be the same as or different from each other. An acyloxy group may be formed.
R _{1 to} R ₄ are a hydrogen atom, a halogen atom, or an organic group. Q _{1 to} Q ₆ are monovalent organic groups, and are bonded by a set of (Q ₁ , Q ₂ ), (Q ₃ , Q ₄ ), (Q ₄ , Q ₅ ), and (Q ₅ , Q ₆ ). May form a ring. )

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

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

Examples of the monovalent organic group represented by the substituents R _{1 to} R ₅ and Q _{1 to} Q ₆ in the present invention include a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ), An alkyl group [represents a linear or branched or cyclic substituted or unsubstituted alkyl group. These are alkyl groups (preferably substituted or unsubstituted alkyl groups having 1 or more carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group Group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group), cycloalkyl group (preferably substituted or non-substituted) Substituted alkyl group having 3 or more carbon atoms, such as cyclopentyl group, cyclobuty Group, a cyclohexyl group, pentafluoro cyclohexyl group) include. Also in the substituents described below, the alkyl group represents an alkyl group of the above concept. ]

  Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 or more carbon atoms, and any one of carbon-carbon single bonds of the above-described alkyl groups having 2 or more carbon atoms being one or more double bonds. For example, ethenyl group (vinyl group), propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 1-octenyl group, 2-octenyl group, 3- Octenyl group, 4-octenyl group, 1,1,1-trifluoro-2-butenyl group), cycloalkenyl group (any carbon of the above-mentioned cycloalkyl group having 2 or more carbon atoms) For example, 1-cycloallyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclo Examples include hexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group, 4-cycloheptenyl group, 3-fluoro-1-cyclohexenyl group, and the like. In the case where a stereoisomer such as a trans (E) isomer and a cis (Z) isomer exists, the alkenyl group may be any of them, and may be a mixture of any ratio thereof. ]

  An alkynyl group (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). Examples include ethynyl group, propargyl group, trimethylsilylethynyl group, and triisopropylsilylethynyl group.)

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

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

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

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

A heteroaryloxy group and a heterothioaryloxy group (preferably a substituted or unsubstituted heteroaryloxy group and a heteroarylthiooxy group, wherein an oxygen atom or a sulfur atom is inserted into the binding site of the heteroaryl group exemplified above; Specific examples include heteroaryloxy groups or heteroarylthioaryloxy groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, thiol groups,
Amino group [preferably amino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted anilino group such as amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenyl Amino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group such as formylamino, acetylamino, pivaloylamino group, lauroylamino, benzoylamino Group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (preferably a carbon-substituted or unsubstituted aminocarbonylamino group such as carbamoylamino group, N, N-dimethyl group) Aminocarboni Amino group, N, N-diethylamino carbonyl amino group include morpholino carbonyl amino group), etc.) and the like.

The monovalent organic group represented by Q _{1 to} Q ₂ can be represented in the same range as R _{1 to} R ₅ , but preferably an aryl group which may have a substituent or More preferably, it is a heteroaryl group, and Q ₁ and Q ₂ form the ring.
Examples of the ring form formed by Q ₁ and Q ₂ include the following structures.

Ｑ_３乃至Ｑ_６についても同様の範囲を取ることが可能であるが、下記一般式（ＩＶ）、（Ｖ）に示されるようにＱ_３乃至Ｑ_６のうち一つ以上が前記アリール基またはヘテロアリール基であるか、またはＱ_３とＱ_４、Ｑ_４とＱ_５、Ｑ_５とＱ_６のうち一つ以上の組が前記アリール基またはヘテロアリール基からなる環を形成していることが好ましい。

Q _{3 to} Q ₆ can have the same range, but as shown in the following general formulas (IV) and (V), at least one of Q _{3 to} Q ₆ is the aryl group or hetero group. It is preferably an aryl group, or at least one of Q ₃ and Q ₄ , Q ₄ and Q ₅ , Q ₅ and Q ₆ forms a ring composed of the aryl group or heteroaryl group .

前記Ａｒは置換基を有していてもよいアリール基またはヘテロアリール基であるが、それらは具体的にはベンゼン環、チオフェン環、ピリジン環、ベンゼン環、ピリジン環、ピラジン環、ピリミジン環、トリアジン環、ピロール環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、フラン環、チオフェン環、セレノフェン環、シロール環が好ましく、より好ましくは、
（ｉ）１つ以上の前記アリール基およびヘテロアリール基、または前記環同士が縮環された化合物、
（ii）（ｉ）の環同士が共有結合を介して連結された化合物、
上記（ｉ）および（ii）より形成される群から少なくとも一つ以上選択される組み合わせで選ばれるπ共役系化合物が好ましく、それらの芳香族炭化水素環または芳香族へテロ環がそれぞれ有するπ電子が、縮環及び共有結合を介した連結による相互作用によって縮環または連結環全体に非局在化した構造であることが好ましい。
ここでの共有結合とは、炭素−炭素単結合、炭素−炭素二重結合、炭素−炭素三重結合、オキシエーテル結合、チオエーテル結合、アミド結合、エステル結合などが挙げられるが、好ましくは前記単結合、二重結合、三重結合のいずれかである。

Ar is an aryl group or heteroaryl group which may have a substituent, and specifically, they are a benzene ring, a thiophene ring, a pyridine ring, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine. Ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, more preferably,
(I) one or more aryl groups and heteroaryl groups, or a compound in which the rings are condensed;
(Ii) a compound in which the rings of (i) are linked via a covalent bond,
A π-conjugated compound selected from a combination selected from at least one selected from the group consisting of (i) and (ii) above is preferred, and the π-electron that each aromatic hydrocarbon ring or aromatic heterocycle has. Is preferably a structure that is delocalized in the condensed ring or the entire linking ring by the interaction by the connection via the condensed ring and the covalent bond.
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.

  The number of aromatic hydrocarbon rings or aromatic heterocycles linked by a condensed ring or a covalent bond is preferably 2 or more. Specifically, naphthalene, anthracene, tetracene, chrysene, pyrene (the following general formula Ar3), pentacene , Thienothiophene (following general formula Ar1), thienodithiophene, triphenylene, hexabenzocoronene, benzothiophene (following general formula Ar2), benzodithiophene, [1] benzothieno [3,2-b] [1] benzothiophene ( BTBT, (the following general formula Ar4), dinaphtho [2,3-b: 2 ′, 3′-f] [3,2-b] thienothiophene (DNTT), benzodithienothiophene (TTPTT, the following general formula Ar5) , Condensed polycyclic compounds such as naphthodithienothiophene (TTNTTT, Ar6, 7), biphenyl, terfeny , Quarter phenyl, bithiophene, terthiophene, oligomers of aromatic hydrocarbon rings and aromatic heterocyclic rings such as quaterthiophene, phthalocyanines, and the like porphyrins.

また、上記一般式中、ｎは１以上の整数であり、Ａｒに対する溶解性置換基の置換数を表わす。一般式（ＩＶ）においては、Ａｒに対して共有結合を介して結合している置換基の数を示す。また、一般式（Ｖ）においては、Ａｒに対して溶解性置換基が縮環構造を取って結合している数を示す。
当然これらはいずれも、Ａｒ上の置換あるいは縮環可能な原子の数に依存する。例えば、無置換のベンゼン環においては、最大で６つの置換位置で共有結合を介して結合が可能であり、最大６カ所で縮環可能である。しかしながら、Ａｒ自体の分子の大きさ、溶解性に応じた置換数、分子の対称性、合成の容易さを考慮すると、下限としてｎは２以上がより好ましい。
ｎがあまりに大きいと、溶解性置換基同士が立体的に混みいりすぎるため好ましくない上に脱離反応前後の体積収縮が大きくなることがあるため、上限としては、分子の対称性、合成の容易さ、溶解性に応じた充分な置換数を考慮すると４以下が好ましい。

In the above general formula, n is an integer of 1 or more, and represents the number of substitutions of the soluble substituent with respect to Ar. In the general formula (IV), the number of substituents bonded to Ar via a covalent bond is shown. In the general formula (V), the number of soluble substituents bonded to Ar through a condensed ring structure is shown.
Of course, both of these depend on the number of atoms that can be substituted or condensed on Ar. 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 Ar itself, the number of substitutions depending on the solubility, the symmetry of the molecule, and the ease of synthesis, n is more preferably 2 or more as the lower limit.
If n is too large, the soluble substituents are sterically mixed together, which is not preferable, and the volume shrinkage before and after the elimination reaction may increase, so the upper limit is molecular symmetry and ease of synthesis. In consideration of a sufficient number of substitutions depending on solubility, 4 or less is preferable.

The acyloxy group (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) preferably has a structure represented by the following general formula (VI).

ｎ＝１の時は下記一般式（ＶＩ−１）のような構造となり、（Ｘ_１，Ｘ_２）または（Ｙ_１，Ｙ_２）は環を形成しておらず、それぞれ独立している。

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

ｎ＝２の時は下記一般式（ＶＩ−２）のような構造となり、（Ｘ_１，Ｘ_２）または（Ｙ_１，Ｙ_２）の位置で置換され、環を形成している。

When n = 2, the structure is represented by the following general formula (VI-2), which is substituted at the position of (X ₁ , X ₂ ) or (Y ₁ , Y ₂ ) to form a ring.

前記Ｒ_５の範囲は前述のとおりであるが、その中においても水素原子（一般式（Ｖ）でｎ＝２のときは除く）、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアルコキシル基、置換または無置換のチオアルキル基、置換または無置換のアリール基、置換または無置換のヘテロアリール基、シアノ基が特に好ましく、より好ましくは水素原子（一般式（Ｖ）でｎ＝２のときは除く）、置換または無置換のアルキル基、置換または無置換のアルコキシル基、置換または無置換のチオアルキル基である。最も好ましくは、置換または無置換のアルキル基、置換または無置換のアルコキシル基のときである。

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

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

The substituent R ₅ in the general formula (V) is not particularly limited, but from the viewpoint of solvent solubility and film formation, the intermolecular interaction as a substituent is reduced to some extent and the affinity with the solvent is increased. However, if the volume change before and after the elimination of the substituent is too great, there is a concern that the thin film may have a problem in the uniformity of the elimination reaction. It is preferable that the substituent is as small as possible while maintaining. Further, although not yet known, R ₅ is an electron-withdrawing substituent (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. It is considered preferable in terms of increasing the efficiency of the separation reaction.

As described above, the substituent-eliminating compound of the present invention has a releasable solvent-soluble substituent, and is characterized by being solubilized in the solvent.
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-conjugated compound A- (C) n in the solvent varies.
Here, “solvent insolubilization” refers to lowering the solubility by one digit or more than the solvent-soluble state. Specifically, with respect to the solvent, in a state where the solvent is heated to reflux and then cooled to room temperature, it is preferable to lower the solubility from 0.05 wt% or more (solvent solubility) to 0.005 wt% or less, More preferably, the solubility is decreased from 0.1 wt% or more (solvent solubility) to 0.01 wt% or less, and the solubility is decreased from 0.5 wt% or more (solvent solubility) to less than 0.05 wt%. Is more preferable, and most preferably, the solubility is decreased 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 actual solvent and temperature used. 25 ° C.).
However, the solvent used in the present invention is not limited thereto.
Since the solubility greatly changes before and after the conversion by the elimination reaction, it becomes difficult to be affected by the solvent used at the time of stacking different films, so that organic thin film transistors, organic EL, organic solar cells, etc. It is useful in the manufacturing process of such an organic electronic device.

  The following compound groups are exemplified as specific structures of the substituent-eliminating compound of the present invention, but the substituent-eliminating compound in the present invention is not limited to these. Moreover, it can be easily inferred that a plurality of stereoisomers having different steric configurations of acyloxy groups exist in the solvent-soluble substituent, and it is also inferred that the following compounds are a mixture thereof.

By applying energy such as heat to the substituent-eliminating compound, a later-described elimination reaction is caused and a specific substituent can be eliminated to obtain the specific compound.
Hereinafter, specific compounds produced from the substituent-elimination compounds shown in the specific examples will be exemplified below, but the specific compounds in the present invention are not limited thereto.

[2. Method for producing specific compound by elimination reaction of substituent-elimination compound]
The elimination reaction will be described in detail.
A leaving component represented by general formulas (IIa) and (IIb) is eliminated from a compound having a cyclohexene ring structure represented by the following general formula (I), and converted to a specific compound having a structure represented by general formula (II).

一般式（Ｉ）で示される化合物には置換基の立体的な配置が異なる異性体が複数存在するが、いずれも一般式（II）で示される特定化合物へと変換され、脱離成分は同一であることに変わりはない。しかし、中でもＸ_１とＹ_１およびＸ_２とＹ_２がシクロヘキサン環平面に対して同一の側にある状態すなわちｃｉｓ構造を取っていることが、脱離反応の効率、変換温度、反応収率の観点からより好ましい。

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 (II), and the elimination components are the same. It remains the same. However, in particular, X ₁ and Y ₁ and X ₂ and Y ₂ are in the same side with respect to the cyclohexane ring plane, that is, taking a cis structure, the efficiency of the elimination reaction, the conversion temperature, and the reaction yield. More preferable from the viewpoint.

(X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) which are groups leaving from the compound (I) are defined as leaving groups, and X ₁ -Y ₁ and X ₂ -Y ₂ are leaving components. Is defined. The desorbing component can take the three states of solid, liquid, and gas, but considering the removal to the outside of the system, the desorbing component is preferably liquid or gas, particularly preferably at room temperature or It becomes a gas at the temperature at which the elimination reaction is carried out.
The boiling point is preferably 500 ° C. or less at atmospheric pressure (1013 hPa). Considering the ease of removal outside the system and the decomposition / sublimation temperature of the π-conjugated compound produced, the boiling point is more preferably 400 ° C. or less. Preferably, it is 300 degrees C or less especially preferably.
In the following, (X ₁ , X ₂ ) is the same acyloxy group, (Y ₁ , Y ₂ ) and R _{1 to} R ₄ are hydrogen atoms, R ₆ is a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy group In the following, an example of the case is shown below, but the substituent-elimination compound of the present invention is not necessarily limited thereto.

上記の例の場合、一般式（ＶII）で示されるシクロヘキセン環構造から、脱離成分として一般式（ＩＸ）で示されるアルキル鎖を有するカルボン酸２分子が脱離し、一般式（ＶIII）で示されるベンゼン環を含む構造に変換される。また、Ｒ_６が置換または無置換のアルコキシ基の場合は、炭酸ハーフエステル（ＩＸ）が不安定であるため、以下に示すようにアルコール（ＩＸ−１）と二酸化炭素（ＩＸ−２）にまで分解されることがある。上記一般式（ＶII）で示される化合物から脱離成分が脱離する機構について以下に概略を示す。

In the case of the above example, from the cyclohexene ring structure represented by the general formula (VII), two molecules of the carboxylic acid having the alkyl chain represented by the general formula (IX) are eliminated as the elimination component, and are represented by the general formula (VIII). Converted to a structure containing a benzene ring. In addition, when R ₆ is a substituted or unsubstituted alkoxy group, the carbonic acid half ester (IX) is unstable, so that the alcohol (IX-1) and carbon dioxide (IX-2) are used as shown below. May be decomposed. An outline of the mechanism by which the desorbing component is desorbed from the compound represented by the general formula (VII) is shown below.

上記一般式（ＶII）に示すように、六員環状の遷移状態を取ることで、β−炭素上の水素原子がカルボニルの酸素原子上へと１，５−転位することで協奏的な脱離反応が起こり、カルボン酸が脱離し、シクロヘキセン環構造から一般式（ＶIII）に示されるようなベンゼン環構造へと変換される。複数の立体異性体が存在する場合においても、反応の速度は違えど、上記反応は進行する。
しかし、中でもアシルオキシ基と水素原子がシクロヘキサン環平面に対して同一の側にある状態すなわちｃｉｓ構造を取っていることが、脱離反応の効率、変換温度、反応収率の観点からより好ましい

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

  Since the extraction and transfer of hydrogen atoms on the β carbon is the first stage of the reaction, the stronger the degree of negative polarization of oxygen atoms, the more likely the reaction will occur. The degree varies depending on, for example, the alkyl chain on the side, and also varies by changing the oxygen atom to a chalcogen atom such as selenium, tellurium or polonium, which is also a group 16 element.

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

Usually, the above 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. In view of energy efficiency, abundance of unconverted molecules, decomposition of the π-electron conjugated compound after conversion, etc., the range of 40 to 500 ° C. is preferable. Furthermore, the thermal stability of the precursor synthesis and the π-electron after conversion In consideration of the decomposition of the conjugated compound and the sublimation temperature, it is more preferably in the range of 80 ° C to 400 ° C, particularly preferably in the range of 80 ° C to 300 ° C.
Here, the sublimation temperature can be defined as a temperature at which a weight loss of 5%, preferably 3% or less, more preferably 1.0%, is observed from the initial weight in TG-DTA, for example. .
Regarding the heating time, the higher the temperature, the shorter the reaction time, and the lower the temperature, the longer the time required for the elimination reaction. Further, although depending on the reactivity and amount of the substituent-eliminating compound, it is usually 0.5 to 120 minutes, preferably 1 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.

  The above acid or base acts as a catalyst for the elimination reaction, and conversion at a lower temperature is possible. The method of using these is not particularly limited, but it may be added as it is to the substituent-eliminating compound, or it may be dissolved in any solvent and added as a solution, or it is vaporized in the atmosphere. 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.

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

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

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

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

  Regarding the method for forming the above-mentioned leaving group, the carboxylic acid ester is converted by reacting an alcohol described later with a carboxylic acid chloride or carboxylic acid anhydride, or by exchange reaction between a halogen atom and a carboxylic acid silver or carboxylic acid-quaternary ammonium salt. In addition to the method of obtaining carbonic acid ester by reacting phosgene with alcohol or by reacting alcohol with carbonic acid half ester such as alkyl chloroformate, after adding carbon disulfide to alcohol, iodination Examples include a method of obtaining xanthate by reacting alkyl, a method of obtaining amine oxide by reacting tertiary amine with hydrogen peroxide or carboxylic acid, and a method of obtaining selenoxide by reacting orthoselenocyanonitrobenzene with alcohol. Limited to Not to.

[3. Method for producing substituent-leaving compound]
The substituent-eliminating compound of the present invention is characterized by having a cyclohexene skeleton and an acyloxy group (this structural part is called a soluble substituent), but this part is not rigid and sterically bulky. For this reason, molecules having poor crystallinity and having this structure often have good solubility and have a property of easily obtaining a film having low crystallinity or an amorphous film when applied from a solution.
Next, a method for forming a halogen group and an acyloxy group in the cyclohexene skeleton of the soluble substituent will be described in detail.

  It can be derived from a compound having a cyclohexene skeleton as shown in the following general formula (X), which can be produced by a conventionally known method and used as a raw material, but from the form of the elimination reaction of the present invention. In view of this, it is preferable to have one or more hydrogen atoms at positions 1, 4 or 2, 3 respectively.

（式中Ｒ_１−Ｒ_４は前記したものと同一の範囲である。）

(Wherein R _{1 to} R ₄ are in the same range as described above.)

Subsequently, as shown in the general formula (XI), the 1, 4-position or the 2, 3-position is selectively halogenated using a brominating agent, but iodine, bromine, A chlorine atom is preferable, and a bromine atom is particularly preferable. Examples of the brominating agent include N-bromosuccinimide, N-iodosuccinimide, N-chlorosuccinimide, and the like, and it is preferable to 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. The halogen compound obtained here can also be used as a substituent elimination compound.

Subsequently, as shown in the general formula (XII), 2 equivalents of silver carboxylate or carboxylic acid quaternary ammonium salt are allowed to act on the dihalogen obtained in the above reaction to obtain the 1, 4-position or 2, A target product in which the 3-position is acyloxylated can be obtained.
In addition, an asymmetric compound can also be obtained by alternately applying 1 equivalent of different carboxylic acid silver salts or carboxylic acid quaternary ammonium salts.
However, since the reaction rates in the elimination reaction may be greatly different, the carboxylic acids used are preferably the same.
Depending on the reaction conditions and the structure of the carboxylic acid used, a plurality of stereoisomers may be produced. Specifically, the racemic mixture and the meso form may be obtained in an arbitrary ratio depending on the configuration of the acyloxy group bonded to the cyclohexene ring. Depending on the steric structure of the acyloxy groups at the 1st, 4th, 2nd and 3rd positions and the hydrogen atom, the elimination reaction may be significantly slowed down. Therefore, a structure in which the reaction proceeds as easily as possible is preferable. That is, it is preferable to be a cis type in which the positional relationship between the 1-position and 2-position or 3-position and 4-position substituents is on the same plane of the cyclohexene plane. On the other hand, the reaction proceeds even in the trans form, but its usefulness is low because it is very slow.
These can be separated by recrystallization or chromatography using an optically active fixed layer. Examples of the carboxylic acid silver salt include silver acetate, silver trifluoroacetate, silver 3,3,3-trifluoropropionate, and the carboxylic acid quaternary ammonium salt includes tetramethylammonium pentahydrate and the above-mentioned. And salts with carboxylic acids (for example, acetic acid, butyric acid, valeric acid, propionic acid, pivalic acid, caproic acid, stearic acid, trifluoroacetic acid, 3,3,3-trifluoropropionic acid). As the solvent, various organic solvents such as dimethylformamide, dithymer sulfoxide, tetrahydrofuran, acetone, and toluene can be used, but in order to prevent reaction rate and side reactions, it is preferable to use a dehydrated solvent. .
Although it is possible to use the reaction temperature from room temperature to the solvent reflux temperature, in order to prevent side reactions such as elimination reaction, it is preferably 50 ° C. or less, and most preferably at room temperature (25 ° C.) or less. .

（式中、Ａｃｙはアシル基を示す。式中Ｒ_１〜Ｒ_４は前記したものと同一の範囲である。）

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

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

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

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

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

  The soluble substituent thus obtained can be condensed by various conventionally known methods to synthesize a substituent-eliminating compound. When this is used as an organic semiconductor precursor compound, for example, in the case of heteroacenes, J. Org. Am. Chem. Soc. In accordance with the method described in 2007, 129, pp2224-2225, etc., it can carry out by the following schemes.

The raw material 1,4-diacyloxy-6-iodo-1,2,3,4-tetrahydronaphthalene 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 added at the same time form a complex, the ortho position (7 position of tetrahydronaphthalene) 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 according to the method described in “Chemical and Functional Phthalocyanine -Chemistry and Function” (edited by IPC, 1997). 1 to 62, Ryo Takahashi, Keiichi Sakamoto, and Eiko Okumura, “Phthalocyanine as a functional dye” (IPC, published in 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.

Moreover, in the substituent compound of the present invention, as a linking method by covalent bond with another skeleton of a solvent-soluble substituent (B in the following general formula), a method by Suzuki coupling reaction, a method by Stille coupling reaction, Performed by using various coupling reactions represented by Kumada coupling reaction, Negishi coupling reaction method, Hiyama coupling reaction method, Sonogashira reaction method, Heck reaction method, Wittig reaction method, etc. The method is exemplified.
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 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 with a combination of a halogen compound and a trifluorotriflate compound represented by the following general formulas (XIII) and (XIV) or a boronic acid derivative and an organotin derivative. However, in the case where both the compounds represented by the general formulas (XV) and (XVI) are a halogen compound, a triflate compound, a boronic acid derivative, and an organotin derivative, a 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.

（上記式（ＸIII）中、Ａｒは前述のアリール基またはヘテロアリール基であり、Ａはハロゲン原子（塩素原子、臭素原子あるいはヨウ素原子を表わす）、トリフラート（トリフルオロメタンスルホニル）基または、ボロン酸またはそのエステルもしくは有機スズ官能基を示す。ｌは１以上の整数である。）

(In the above formula (XIII), Ar is the aryl group or heteroaryl group described above, and A is a halogen atom (representing a chlorine atom, bromine atom or iodine atom), a triflate (trifluoromethanesulfonyl) group, a boronic acid or The ester or organotin functional group is represented by l being an integer of 1 or more.)

（上記式（ＸＩＶ）中、Ｂは前述の溶媒可溶性置換基、Ｃはハロゲン原子（塩素原子、臭素原子あるいはヨウ素原子を表わす）、トリフラート（トリフルオロメタンスルホニル）基または、ボロン酸またはそのエステルもしくは有機スズ官能基を示す。ｋは１以上の整数である。）

(In the above formula (XIV), B is the aforementioned solvent-soluble substituent, C is a halogen atom (representing a chlorine atom, bromine atom or iodine atom), a triflate (trifluoromethanesulfonyl) group, boronic acid, its ester or organic Represents a tin functional group, k is an integer of 1 or more.)

  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 (XIII) and (XIV).

As the organotin functional group in the general formulas (XIII) and (XIV), 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 the hydrogen or halogen atom at a desired position with lithium or a Grineer 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 the substituent Ar or B may be a halogen and a triflate, or a boronic acid derivative and an organotin derivative. However, in terms of ease of derivatization and reduction of side reactions, the substituent A is preferred. 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 (PPh3) 2], tetrakis (triphenylphosphine) palladium [Pd (PPh3) 4], dichlorobis (acetonitrile) palladium [Pd (CH3CN) 2Cl2], dichlorobis (benzonitrile) palladium [Pd (PhCN) ) 2 Cl2], dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) Cl2], dichloro [1,1-bis (diphenylphosphino) ferro ] Palladium [Pd (dppf) Cl2], dichlorobis (tricyclohexylphosphine) palladium [Pd [P (C6 H1 1) 3] 2 Cl2], dichlorobis (triphenylphosphine) palladium [Pd (PPh3) 2 Cl2], tris (Dibenzylideneacetone) dipalladium [Pd2 (dba) 3], bis (dibenzylideneacetone) palladium [Pd (dba) 2], and the like, and tetrakis (triphenylphosphine) palladium [Pd (PPh3) 4]. A phosphine-based catalyst such as dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) Cl2], dichlorobis (triphenylphosphine) palladium [Pd (PPh3) 2Cl2], and the like is preferable.

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

  The substituent-eliminating compound represented by Ar- (B) m (m is an integer of 1 or more) obtained as described above is the catalyst used in the reaction, the unreacted raw material, and the boronic acid produced as a by-product during the reaction. It is used after removing impurities such as salts and organotin derivatives. 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. As described above, a material having excellent solubility, such as the compound of the present invention, has less restrictions on the purification method, and consequently has a positive effect on device characteristics.

  In order to make the substituent-eliminating compound obtained by the above-described manufacturing method into a thin film, known film formation such as spin coating method, casting method, dipping method, ink jet method, doctor blade method, screen printing method, vacuum deposition, sputtering, etc. The method can be used. Thereby, it is possible to produce a good thin film excellent in strength, toughness, durability, etc. without cracks. Furthermore, by applying an external stimulus to the film of the substituent-eliminating compound of the present invention applied by the above-described film-forming method, it is possible to desorb soluble substituents and form an organic semiconductor film. It can be suitably used as a material for various functional elements such as an element, a thin film transistor element, and a light emitting element.

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

  An example of an electronic device suitable for applying the substituent leaving compound of the present invention and the organic semiconductor compound produced therefrom is an organic thin film transistor, that is, an organic field effect transistor (OFET). Hereinafter, this FET will be described in detail.

"Transistor structure"
4A to 4D are schematic structures of the organic thin film transistor according to the present invention. The organic semiconductor layer (1) of the organic thin film transistor according to the present invention contains the organic semiconductor compound 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. The switching element includes a gate electrode (4). 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”
In addition, by using the substituent elimination compound of the present invention as an organic semiconductor precursor, it is dissolved in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene and xylene, and coated on a support. It can also be formed by forming a thin film made of an organic semiconductor precursor and then applying energy to this film to convert it into an organic semiconductor film.
The substituent-eliminating compound of the present invention has a cyclohexene structure and an acyloxy group, and since this part is sterically bulky, a molecule having this structure with poor crystallinity has good solubility and is out of solution. When applied, it has a property that an amorphous film having low crystallinity or an amorphous state 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 include printing methods such as letterpress printing and flexographic printing, and soft lithography techniques such as microcontact printing, and a combination of these techniques can also be used. And according to material, a suitable solvent is selected from the said suitable film forming method and the said solvent. In addition, the organic semiconductor material itself after heat conversion can be formed into a vapor phase such as a vacuum deposition method.

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, no gap or hole that adversely affects the carrier transport property of the organic semiconductor layer) is formed. The thickness is selected.
The thickness of the organic semiconductor thin film is generally 1 μm or less, particularly preferably 5 to 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 method can also be used.
Moreover, the organic thin-film transistor of this invention can provide the extraction electrode from each electrode as needed.

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

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

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

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

"Organic semiconductor / insulating film 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 a protective layer is used as necessary for protection from mechanical destruction, protection from moisture and gas, or protection for the convenience of device integration. Can also be provided.

"Applied devices"
The organic thin film transistor of the present invention 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 a switching element for applying a voltage or supplying a 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 form apply voltage or current to the corresponding display elements. By configuring so that the switch is turned on or off only when supplying, and turned off or on at other times, the display device can display 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 applying a voltage to the liquid crystal to control the molecular arrangement of the liquid crystal. In the case of the organic or inorganic electroluminescence 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.
The identification of the compounds in the following examples is performed by NMR spectrum (JNM-ECX (trade name) 500 MHz, manufactured by JEOL Ltd.), mass spectrometry (GCMS-QP2010 Plus (trade name), manufactured by Shimadzu Corporation), elemental analysis (CHN) ( CHN recorder MT-2 (manufactured by Yanagimoto Seisakusho), elemental analysis (sulfur) (ion chromatography → anion analysis system DX320 (trade name), manufactured by Dionex) was used. The purity of the compound was calculated from the peak area ratio using mass spectrometry (GCMS-QP2010 Plus (trade name), manufactured by Shimadzu Corporation) or LCMS (LCT Premier and Alliance (trade name), manufactured by Waters).

[Synthesis Example 1]
[Synthesis of Specific Compound Intermediate 1]
・ Synthesis of Compound 2

５００ｍＬのビーカーに１，２，３，４−ｔｅｔｒａｈｙｄｒｏ−６−ｉｏｄｏ ｎａｐｈｔｈａｌｅｎｅ（上記式１の化合物、１０ｇ，６５．３ｍｍｏｌ）と１５％ＨＣｌ（６０ｍＬ）を入れ、氷冷却下５℃以下を維持しながら、亜硝酸ナトリウム水溶液（５．４１ｇ，７８．３６ｍｍｏｌ ｉｎ Ｗａｔｅｒ ２３ｍＬ）を徐々に滴下した。
滴下終了後、そのままの温度で１時間攪拌し、ヨウ化カリウム水溶液（１３．０ｇ，７８．３６ｍｍｏｌ ｉｎ Ｗａｔｅｒ ５０ｍＬ）を一度に加え、氷浴を外し３時間攪拌し、その後６０℃で窒素の発生が収まるまで１時間加熱した。
室温まで冷却した後、反応溶液をジエチルエーテルで３回抽出した。有機層を５％チオ硫酸ナトリウム水溶液（１００ｍＬ×３回）で洗浄し、さらに飽和食塩水（１００ｍＬ×２回）で洗浄した。さらに、硫酸ナトリウムで乾燥させ、濾液を濃縮することで赤色のオイルを得た。
これをシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン）にて精製することにより、無色のオイルとして化合物２を得た。（収量１２．０ｇ，収率７１．２％）
以下に化合物２の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：１．７３−１．８１（ｍ，４Ｈ），２．７０（ｑｕｉｎｔ，４Ｈ，Ｊ＝４．８５Ｈｚ），６．８０（ｄ，１Ｈ，Ｊ＝８．０Ｈｚ），７．３８（ｄｄ，１Ｈ，Ｊ_１＝８．０Ｈｚ Ｊ_２＝１．７５Ｈｚ），７．４１（ｓ，１Ｈ）
質量分析：ＧＣ−ＭＳｍ／ｚ＝２５８（Ｍ＋）

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

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

１００ｍＬの丸底フラスコに化合物２（３．１ｇ，１２ｍｍｏｌ）、アゾビスイソブチロニトリル（５９ｍｇ，０．３６ｍｍｏｌ）、四塩化炭素（５０ｍＬ）、Ｎ−ブロモスクシンイミド（４．７ｇ，２６．４ｍｍｏｌ）を入れ、アルゴンガスで置換を行なった後、穏やかに８０℃に加熱し、そのまま１時間攪拌し、室温まで冷却した。沈殿を濾過し、濾液を減圧下で濃縮することで、薄黄色の固体として化合物３を得た。（収量４．９９ｇ，収率１００％）
これ以上精製することなく次の反応に用いた。
以下に化合物３の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：２．３１−２．４１（ｍ，２Ｈ），２．７０−２．７９（ｍ，２Ｈ），５．６５（ｔ，２Ｈ，Ｊ＝２．０Ｈｚ），７．２４−７．２８（ｍ，２Ｈ），７．３１−７．３４（ｍ，２Ｈ）
質量分析：ＧＣ−ＭＳｍ／ｚ＝４１３（Ｍ＋）

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

Synthesis of Compound 1, 1,4-dibromo-1,2,3,4-tetrahydronaphthalene is similar to Compound 3 in J. Org. Chem. Those synthesized by the method described in 1999, 64, 9365-9373 were used as raw materials.

１００ｍＬの丸底フラスコにテトラメチルアンモニウムヒドロキシド５水和物（３．６２ｇ，２０ｍｍｏｌ）、酢酸（１．２１ｇ，２０ｍｍｏｌ）、ジメチルホルムアミド（以下ＤＭＦ）（３０ｍＬ）を入れ、アルゴン置換した後、室温で２．５時間攪拌した。そこへ、１，４−ｄｉｂｒｏｍｏ−１，２，３，４−ｔｅｔｒａｈｙｄｒｏｎａｐｈｔｈａｌｅｎｅ（２．９０ｇ，１０ｍｍｏｌ）を加え、さらに室温で１６時間攪拌した。反応溶液を酢酸エチル１００ｍＬで希釈し、純水２００ｍＬを加え、有機層を分離した。水層は酢酸エチル３０ｍＬで４回抽出し合わせた有機層を飽和炭酸水素ナトリウム溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。濾液を濃縮し、薄い褐色の固体を得た。これをヘキサンで洗浄し、無色の固体として化合物４を得た。（収量１．５０ｇ，収率６０．６％、ラセミ体とメソ体の５：６の混合物）
ヘキサンから再結晶することで、ラセミ体とメソ体をそれぞれ分離した。
以下に化合物４の分析結果を示す。
［ラセミ体］
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：１．９６−１．９９（ｍ，２Ｈ），２．０７（ｓ，６Ｈ），２．２７−２．３０（ｍ，２Ｈ），６．０５（ｔ，２Ｈ，Ｊ＝２．３Ｈｚ），７．３４（ｂｒ，４Ｈ）
［メソ体］
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：２．０９−２．１２（ｍ，４Ｈ），２．１３（ｓ，６Ｈ），５．９６−５．９８（ｍ，２Ｈ），７．３２（ｂｒ，４Ｈ）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝２４８（Ｍ＋）

A 100 mL round bottom flask was charged with tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), acetic acid (1.21 g, 20 mmol), dimethylformamide (hereinafter DMF) (30 mL), purged with argon, For 2.5 hours. 1,4-dibromo-1,2,3,4-tetrahydronaphthalene (2.90 g, 10 mmol) was added thereto, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a light brown solid. This was washed with hexane to obtain Compound 4 as a colorless solid. (Yield 1.50 g, Yield 60.6%, 5: 6 mixture of racemate and meso form)
By recrystallization from hexane, the racemate and meso form were separated.
The analysis results of Compound 4 are shown below.
[Racemic]
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.96-1.99 (m, 2H), 2.07 (s, 6H), 2.27-2.30 (m, 2H), 6 .05 (t, 2H, J = 2.3Hz), 7.34 (br, 4H)
[Meso body]
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.09-2.12 (m, 4H), 2.13 (s, 6H), 5.96-5.98 (m, 2H), 7 .32 (br, 4H)
Mass spectrometry: GC-MS m / z = 248 (M +)

  Synthesis of compound 5

１００ｍＬの丸底フラスコにテトラメチルアンモニウムヒドロキシド５水和物（３．６２ｇ，２０ｍｍｏｌ）、カプロン酸（２．５１ｍＬ，２０ｍｍｏｌ）、ＤＭＦ（３０ｍＬ）を入れ、アルゴン置換した後、室温で２．５時間攪拌した。そこへ、化合物３（４．１６ｇ，１０ｍｍｏｌ）を加え、さらに室温で１６時間攪拌した。反応溶液を酢酸エチル１００ｍＬで希釈し、純水２００ｍＬを加え、有機層を分離した。水層は酢酸エチル３０ｍＬで４回抽出し合わせた有機層を飽和炭酸水素ナトリウム溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。濾液を濃縮し、オレンジ色のオイルを得た。これをシリカゲルカラムクロマトグラフィー（溶媒：トルエン→酢酸エチル／トルエン（５／９５，ｖ／ｖ））にて精製することにより、無色のオイルとして化合物５を得た。（収量２．４４ｇ，収率５０．２％）
以下に化合物５の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：０．８７−０．９０（ｍ，６Ｈ），１．２４−１．３４（ｍ，８Ｈ），１．６０−１．６７（ｍ，４Ｈ），１．９０−１．９４（ｍ，２Ｈ），２．２３−２．３４（ｍ，６Ｈ），５．９８（ｄ，２Ｈ，Ｊ＝３．５Ｈｚ），７．０６（ｄ，２Ｈ，Ｊ＝８．０Ｈｚ），７．６３−７．６６（ｍ，２Ｈ）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝４８６（Ｍ＋）
以上の分析結果から、合成したものが、化合物５の構造と矛盾がないことを確認した。

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

Synthesis of compound 6

１００ｍＬの丸底フラスコにテトラメチルアンモニウムヒドロキシド５水和物（３．６２ｇ，２０ｍｍｏｌ）、ピバル酸（２．０４ｇ，２０ｍｍｏｌ）、ＤＭＦ（３０ｍＬ）を入れ、アルゴン置換した後、室温で２．５時間攪拌した。そこへ、化合物３（４．１６ｇ，１０ｍｍｏｌ）を加え、さらに室温で１６時間攪拌した。反応溶液を酢酸エチル１００ｍＬで希釈し、純水２００ｍＬを加え、有機層を分離した。水層は酢酸エチル３０ｍＬで４回抽出し、合わせた有機層を飽和炭酸水素ナトリウム溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。濾液を濃縮し、薄いオレンジ色の固体を得た。これをエタノールから再結晶（繰り返し２回）することで、薄黄色の結晶として化合物６を得た。（収量１．９３ｇ，収率４２．０％）
以下に化合物６の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：１．１８（ｓ，１８Ｈ），１．２０（ｓ，１８Ｈ），１．８７−１．９２（ｍ，４Ｈ），２．２１−２．２４（ｍ，４Ｈ），５．９４（ｄ，４Ｈ，Ｊ＝２．３Ｈｚ），７．０２（ｄ，２Ｈ，Ｊ＝８．０Ｈｚ），７．６２−７．６３（ｍ，２Ｈ），７．６４−７．６５（ｍ，２Ｈ）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝４５８（Ｍ＋）
融点：１１４．０−１１５．５℃
以上の分析結果から、合成したものが、化合物６の構造と矛盾がないことを確認した。

A 100 mL round bottom flask was charged with tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), pivalic acid (2.04 g, 20 mmol), DMF (30 mL), purged with argon, and then 2.5 mL at room temperature. Stir for hours. Thereto, Compound 3 (4.16 g, 10 mmol) was added, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layers were washed with saturated sodium bicarbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a pale orange solid. This was recrystallized from ethanol (repeated twice) to obtain Compound 6 as pale yellow crystals. (Yield 1.93 g, Yield 42.0%)
The analysis results of Compound 6 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.18 (s, 18H), 1.20 (s, 18H), 1.87-1.92 (m, 4H), 2.21-2 .24 (m, 4H), 5.94 (d, 4H, J = 2.3 Hz), 7.02 (d, 2H, J = 8.0 Hz), 7.62-7.63 (m, 2H) , 7.64-7.65 (m, 2H)
Mass spectrometry: GC-MS m / z = 458 (M +)
Melting point: 114.0-115.5 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 6.

Synthesis of compound 7

１００ｍＬの丸底フラスコにテトラメチルアンモニウムヒドロキシド５水和物（３．６２ｇ，２０ｍｍｏｌ）、３，３，３−トリフルオロプロパン酸（２．５６ｇ，２０ｍｍｏｌ）、ＤＭＦ（３０ｍＬ）を入れ、アルゴン置換した後、室温で２．５時間攪拌した。そこへ、化合物３（４．１６ｇ，１０ｍｍｏｌ）を加え、さらに室温で４８時間攪拌した。
反応溶液を酢酸エチル１００ｍＬで希釈し、純水２００ｍＬを加え、有機層を分離した。水層は酢酸エチル３０ｍＬで４回抽出し、合わせた有機層を飽和炭酸水素ナトリウム溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。濾液を濃縮し、褐色の液体を得た。これをシリカゲルカラムクロマトグラフィー（溶媒：酢酸エチル／ヘキサン（１／２，ｖ／ｖ）＋２％トリエチルアミン添加）にて精製することにより、淡黄色のオイルを得た。（収量２．４４ｇ）
さらにリサイクル分取ＨＰＬＣ（日本分析工業社製、ＬＣ−９１０４）にて精製することにより、無色のオイルとして化合物７を得た（収量１．２ｇ，収率２５％）

A 100 mL round bottom flask was charged with tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), 3,3,3-trifluoropropanoic acid (2.56 g, 20 mmol), DMF (30 mL), and purged with argon. And then stirred at room temperature for 2.5 hours. Thereto, Compound 3 (4.16 g, 10 mmol) was added, and the mixture was further stirred at room temperature for 48 hours.
The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layers were washed with saturated sodium bicarbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a brown liquid. This was purified by silica gel column chromatography (solvent: ethyl acetate / hexane (1/2, v / v) + 2% triethylamine added) to obtain a pale yellow oil. (Yield 2.44 g)
Furthermore, it refine | purified by recycle preparative HPLC (the product made by Japan Analytical Industrial Co., Ltd., LC-9104), and the compound 7 was obtained as a colorless oil (yield 1.2g, 25% of yield).

The analysis results of Compound 7 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.99-2.31 (m, 4H, H2, H3), 3.14-3.30 (m, 4H, —CH 2 CF 3), 5.96 −6.08 (m, 2H, H1, H4), 7.05-7.10 (m, 1H, ArH), 7.66-7.71 (m, 2H, ArH) Mass spectrometry: GC-MS m / Z = 510 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 7.

[Synthesis Example 2]
[Synthesis of Compound Intermediate 2]
Synthesis of compound 8

充分に乾燥させた２００ｍＬの丸底フラスコに、チエノ［３，２−ｂ］チオフェン（２．８１ｇ，２０．０ｍｍｏｌ）を入れ、アルゴン置換を行なった後、脱水テトラヒドロフラン（以下ＴＨＦ）（５０ｍＬ）を加え、アセトン−ドライアイス浴で−７８℃まで冷却し、ｎ−ブチルリチウム（２．２ｅｑ，２８．１ｍＬ（１．６Ｍヘキサン溶液），４４ｍｍｏｌ）を１５分かけて滴下し、反応系内を室温まで昇温し、そのまま１６時間攪拌を行なった。再び−７８℃に冷却し、トリメチルスズクロリド（２．５ｅｑ，５０ｍＬ（１．０Ｍヘキサン溶液），５０ｍｍｏｌ）を一度に加え、反応系内を室温まで昇温させ、２４時間攪拌を行なった。
水（８０ｍＬ）を加えて、クエンチし、酢酸エチルを加えて有機層を分離した。有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、さらに硫酸ナトリウムで乾燥を行ない、濾液を濃縮し、褐色の固体を得た。これをアセトニトリルから再結晶（繰り返し３回）することにより、無色の結晶として化合物８を得た。（収量５．０ｇ，５４．１％）
以下に化合物８の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：０．３８（ｓ，１８Ｈ），７．２３（ｓ，２Ｈ）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝４６６（Ｍ＋）
以上の分析結果から、合成したものが、化合物８の構造と矛盾がないことを確認した。

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 THF) (50 mL) was added. In addition, the mixture was 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, and the reaction system was cooled to room temperature. The mixture was heated up to 16 hours 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 Benzo [1,2-b: 4,5-b ′] dithiophene is prepared according to the method described in J.P. Org. Chem. , 2005, 70 (25), pp1069-10571 and Org. Lett. What was synthesize | combined according to the method of 2009,11 (11), pp2473-475 was used as a raw material.

充分に乾燥させた２００ｍＬの丸底フラスコに、ベンゾ［１，２−ｂ：４，５−ｂ’］ジチオフェン（３．８１ｇ，２０．０ｍｍｏｌ）を入れ、アルゴン置換を行なった後、脱水ＴＨＦ（５０ｍＬ）を加え、アセトン−ドライアイス浴で−７８℃まで冷却し、ｎ−ブチルリチウム（２．２ｅｑ，２８．１ｍＬ（１．６Ｍヘキサン溶液），４４ｍｍｏｌ）を１５分かけて滴下し、反応系内を室温まで昇温し、そのまま１６時間攪拌を行なった。再び−７８℃に冷却し、トリメチルスズクロリド（２．５ｅｑ，５０ｍＬ（１．０Ｍヘキサン溶液），５０ｍｍｏｌ）を一度に加え、反応系内を室温まで昇温させ、２４時間攪拌を行なった。
水（８０ｍＬ）を加えて、クエンチし、酢酸エチルを加えて有機層を分離した。有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、さらに硫酸ナトリウムで乾燥を行ない、濾液を濃縮し、褐色の固体を得た。これをアセトニトリルから再結晶（繰り返し３回）することにより、薄黄色の結晶として化合物９を得た。（収量７．４８ｇ，７２．５％）

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 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 9 as pale yellow crystals. (Yield 7.48 g, 72.5%)

The analysis results of Compound 9 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.44 (s, 18H), 7.41 (s, 2H), 8.27 (s, 2H)
Mass spectrometry: GC-MS m / z = 518 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 9.

Synthesis of Compound 10 2,7-Diiodo [1] benzothieno [3,2-b] [1] benzothiophene is described in Zh. Org. Khim. 16, 2, 383 (1980) and J.A. Am. Chem. Soc. 128,12604 (2006) was used as a raw material.

充分に乾燥させた３００ｍＬの丸底フラスコに、２，７−ジヨード［１］ベンゾチエノ［３，２−ｂ］［１］ベンゾチオフェン（４．９２ｇ，１０．０ｍｍｏｌ）を入れ、アルゴン置換を行なった後、脱水ＴＨＦ（１５０ｍＬ）を加え、アセトン−ドライアイス浴で−７８℃まで冷却し、ｎ−ブチルリチウム（２．２ｅｑ，１４．１ｍＬ（１．６Ｍヘキサン溶液），２２ｍｍｏｌ）を１５分かけて滴下し、反応系内を室温まで昇温し、そのまま１６時間攪拌を行なった。再び−７８℃に冷却し、トリメチルスズクロリド（２．５ｅｑ，２５ｍＬ（１．０Ｍヘキサン溶液），２５ｍｍｏｌ）を一度に加え、反応系内を室温まで昇温させ、２４時間攪拌を行なった。
水（８０ｍＬ）を加えて、クエンチし、クロロホルムを加えて有機層を分離した。有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、さらに硫酸ナトリウムで乾燥を行ない、濾液を濃縮し褐色の固体を得た。これをトルエン、続けてアセトニトリルから再結晶することにより、薄褐色の結晶として化合物１０を得た。（収量３．４０ｇ，６０．０％）
以下に化合物１０の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：０．３７（ｓ，１８Ｈ），７．５５（ｄ，２Ｈ，Ｊ＝８．６Ｈｚ），７．８７（ｄ，２Ｈ，Ｊ＝７．５Ｈｚ），８．０４（ｓ，２Ｈ）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝５６６（Ｍ＋）
以上の分析結果から、合成したものが、化合物１０の構造と矛盾がないことを確認した。

2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.92 g, 10.0 mmol) was placed in a well-dried 300 mL round bottom flask, and purged with argon. Thereafter, dehydrated THF (150 mL) was added, and the mixture was cooled to −78 ° C. in an acetone-dry ice bath, and n-butyllithium (2.2 eq, 14.1 mL (1.6 M hexane solution), 22 mmol) was added over 15 minutes. The reaction system was dropped to room temperature and stirred for 16 hours. The mixture was cooled again to −78 ° C., trimethyltin chloride (2.5 eq, 25 mL (1.0 M hexane solution), 25 mmol) was added 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 chloroform 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 toluene, followed by acetonitrile to obtain Compound 10 as light brown crystals. (Yield 3.40 g, 60.0%)
The analysis results of Compound 10 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.37 (s, 18H), 7.55 (d, 2H, J = 8.6 Hz), 7.87 (d, 2H, J = 7. 5Hz), 8.04 (s, 2H)
Mass spectrometry: GC-MS m / z = 566 (M +)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 10.

[Synthesis Example 3]
[Synthesis of precursor molecules]
Synthesis of compound 11

In a 100 mL round bottom flask, compound 5 (973 mg, 2.0 mmol), compound 8 (466 mg, 1 mmol) and DMF (10 mL) were placed, and after argon gas was bubbled for 30 minutes, tris (dibenzylideneacetone) dipalladium ( 0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at room temperature for 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 give Compound 11 as a yellow solid (yield 680 mg, yield 79.3%).
The compound analysis results are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.87-0.89 (m, 12H), 1.28-1.33 (m, 16H), 1.61-1.69 (m, 8H), 1.96-2.01 (m, 4H), 2.28-2.36 (m, 12H), 6.08 (d, 4H, J = 12.1 Hz), 7.37 (d, 2H, J = 8.6 Hz), 7.48 (s, 2H), 7.57-7.59 (m, 4H)
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 Compound 11.

Synthesis of compound 12

１００ｍＬの丸底フラスコに、化合物６（２．０ｍｍｏｌ，９１７ｍｇ）、化合物８（４６６ｍｇ，１ｍｍｏｌ）、ＤＭＦ（１０ｍＬ）を入れ、アルゴンガスを３０分間バブリングした後、トリス（ジベンジリデンアセトン）ジパラジウム（０）（１８．３ｍｇ，０．０２ｍｍｏｌ）、トリ（オルトトリル）ホスフィン（２４．４ｍｇ，０．０８ｍｍｏｌ）を加え、アルゴン雰囲気下室温で２４時間、続けて５０℃で３時間攪拌した。反応溶液をトルエンで希釈し、セライト濾過で不溶物を除去し、濾液に水を加え、有機層を分離した。水層はトルエンで抽出を行なった。合わせた有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させ、濾液を濃縮し得られた固体をヘキサンで洗浄することにより、黄色の固体として化合物を得た。（収量３２０ｍｇ，収率４０．０％）
以下に化合物１２の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：１．２１（ｓ，１８Ｈ），１．２４（ｓ，１８Ｈ），１．９０−１．９６（ｍ，４Ｈ），２．３０（ｄｔ，４Ｈ，Ｊ_１＝９．２Ｈｚ，Ｊ_２＝２．３Ｈｚ），６．０３（ｄ，４Ｈ，Ｊ＝１３．２Ｈｚ），７．３２（ｄ，２Ｈ，Ｊ＝８．０Ｈｚ７．４６（ｓ，２Ｈ），７．５３（ｄ，２Ｈ，Ｊ＝１．７Ｈｚ），７．５８（ｄｄ，２Ｈ，Ｊ_１＝８．０Ｈｚ，Ｊ_２＝２．３Ｈｚ）
元素分析（Ｃ_４６Ｈ_５６Ｏ_８Ｓ_２）：Ｃ，６８．８７；Ｈ，６．９５；Ｏ，１６．０８；Ｓ，８．１０（実測値）、Ｃ，６８．９７；Ｈ，７．０５；Ｏ，１５．９８；Ｓ，８．０１（理論値）
分解点：２７５．２℃
以上の分析結果から、合成したものが、化合物１２の構造と矛盾がないことを確認した。

In a 100 mL round bottom flask, compound 6 (2.0 mmol, 917 mg), compound 8 (466 mg, 1 mmol), and DMF (10 mL) were placed, and after argon gas was bubbled for 30 minutes, tris (dibenzylideneacetone) dipalladium ( 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 24 hours and then at 50 ° C. for 3 hours under an argon atmosphere. The reaction solution was diluted with toluene, insoluble materials were removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with toluene. The combined organic layers were washed with a saturated aqueous potassium fluoride solution, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to obtain a compound as a yellow solid by washing with hexane. . (Yield 320 mg, Yield 40.0%)
The analysis results of Compound 12 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.21 (s, 18H), 1.24 (s, 18H), 1.90-1.96 (m, 4H), 2.30 (dt , 4H, J ₁ = 9.2 Hz, J ₂ = 2.3 Hz), 6.03 (d, 4H, J = 13.2 Hz), 7.32 (d, 2H, J = 8.0 Hz 7.46 (s , 2H), 7.53 (d, 2H, J = 1.7 Hz), 7.58 (dd, 2H, J ₁ = 8.0 Hz, J ₂ = 2.3 Hz)
Elemental analysis _{(C 46 H 56 O 8 S} 2): C, 68.87; H, 6.95; O, 16.08; S, 8.10 ( Found), C, 68.97; H, 7 .05; O, 15.98; S, 8.01 (theoretical value)
Decomposition point: 275.2 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 12.

Synthesis of compound 13

１００ｍＬの丸底フラスコに、化合物７（１０２０ｍｇ，２．０ｍｍｏｌ）、化合物８（４６６ｍｇ，１ｍｍｏｌ）、ＤＭＦ（１０ｍＬ）を入れ、アルゴンガスを３０分間バブリングした後、トリス（ジベンジリデンアセトン）ジパラジウム（０）（１８．３ｍｇ，０．０２ｍｍｏｌ）、トリ（オルトトリル）ホスフィン（２４．４ｍｇ，０．０８ｍｍｏｌ）を加え、アルゴン雰囲気下室温で１６時間、続けて８０℃で８時間攪拌した。反応溶液を酢酸エチルで希釈し、セライト濾過で不溶物を除去し、濾液に水を加え、有機層を分離した。水層は酢酸エチルで抽出を行なった。合わせた有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させ、濾液を濃縮し、黄色の固体を得た。これをカラムクロマトグラフィー（固定層：（中性シリカゲル（関東化学製）＋１０ｗｔ％フッ化カリウム，溶媒：ヘキサン／酢酸エチル（２／１，ｖ／ｖ）＋２％トリエチルアミン添加）にて精製することにより、黄色の固体を得た。
さらにリサイクル分取ＨＰＬＣ（日本分析工業社製，ＬＣ−９１０４，溶媒：ＴＨＦ）にて精製することにより、淡黄色の結晶として化合物１３を得た（収量２００ｍｇ，収率２２．１％）
以下に化合物１３の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：２．０６−２．３５（ｍ，８Ｈ，Ｈ２，Ｈ３ ｏｆ Ｔｅｔｒａｌｉｎ），３．１６−３．３．３３（ｍ，８Ｈ，−ＣＨ２ＣＦ３），６．０７−６．１８（ｍ，４Ｈ，Ｈ１，Ｈ４ ｏｆ Ｔｅｔｒａｌｉｎ），７．３６−７．４１（ｍ，２Ｈ，ＡｒＨ），７．５０（ｄ，２Ｈ，Ｊ＝６．９Ｈｚ，ＡｒＨ），７．５７−７．６４（ｍ，４Ｈ，ＡｒＨ）
元素分析（Ｃ_３８Ｈ_２８Ｆ_１２Ｏ_８Ｓ_２）：Ｃ，５０．６５；Ｈ，３．０２；Ｏ，１４．００；Ｓ，７．１９（実測値）、Ｃ，５０．４５；Ｈ，３．１２；Ｏ，１４．１５；Ｓ，７．０９（理論値）
分解点：１９７．５℃
以上の分析結果から、合成したものが、化合物１３の構造と矛盾がないことを確認した。

In a 100 mL round bottom flask, compound 7 (1020 mg, 2.0 mmol), compound 8 (466 mg, 1 mmol) and DMF (10 mL) were placed, and after argon gas was bubbled for 30 minutes, tris (dibenzylideneacetone) dipalladium ( 0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at room temperature for 16 hours and then at 80 ° C. for 8 hours under an argon atmosphere. The reaction solution was diluted with ethyl acetate, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. By purifying this with column chromatography (fixed layer: (neutral silica gel (manufactured by Kanto Chemical) + 10 wt% potassium fluoride, solvent: hexane / ethyl acetate (2/1, v / v) + 2% triethylamine added)) A yellow solid was obtained.
Furthermore, the compound 13 was obtained as a pale yellow crystal | crystallization by refine | purifying with recycle preparative HPLC (The Nippon Analytical Industrial company make, LC-9104, solvent: THF) (yield 200 mg, yield 22.1%).
The analysis results of Compound 13 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.06-2.35 (m, 8H, H 2, H 3 of Tetralin), 3.16-3.33 (m, 8H, —CH 2 CF 3) 6.07-6.18 (m, 4H, H1, H4 of Tetralin), 7.36-7.41 (m, 2H, ArH), 7.50 (d, 2H, J = 6.9 Hz, ArH) ), 7.57-7.64 (m, 4H, ArH)
Elemental analysis _{(C 38 H 28 F 12 O} 8 S 2): C, 50.65; H, 3.02; O, 14.00; S, 7.19 ( Found), C, 50.45; H 3.12; O, 14.15; S, 7.09 (theoretical value)
Decomposition point: 197.5 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 13.

Synthesis of compound 14

１００ｍＬの丸底フラスコに、化合物７（１８８７ｍｇ，３．７ｍｍｏｌ）、化合物９ （９２９ｍｇ，１．８ｍｍｏｌ）、ＤＭＦ（２５ｍＬ）を入れ、アルゴンガスを３０分間バブリングした後、トリス（ジベンジリデンアセトン）ジパラジウム（０）（３２．９ｍｇ，０．０３６ｍｍｏｌ）、トリ（オルトトリル）ホスフィン（４３．９ｍｇ，０．１４４ｍｍｏｌ）を加え、アルゴン雰囲気下８０℃で４時間攪拌した。反応溶液をクロロホルムで希釈し、セライト濾過で不溶物を除去し、濾液に水を加え、有機層を分離した。水層はクロロホルムで抽出を行なった。合わせた有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させ、濾液を濃縮し、黄色の固体を得た。
これをリサイクル分取ＨＰＬＣ（日本分析工業社製，ＬＣ−９１０４，溶媒：ＴＨＦ）にて精製することにより、淡黄色の結晶として化合物１４を得た（収量３４０ｍｇ，収率２０．０％）
以下に化合物１４の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：２．０８−２．３７（ｍ，８Ｈ，Ｈ２，Ｈ３ ｏｆ Ｔｅｔｒａｌｉｎ），３．２０−３．３．３４（ｍ，８Ｈ，−ＣＨ２ＣＦ３），６．０９−６．６．２１（ｍ，４Ｈ，Ｈ１，Ｈ４ ｏｆ Ｔｅｔｒａｌｉｎ），７．４０−７．４７（ｍ，２Ｈ，ＡｒＨ），７．６０（ｄ，２Ｈ，Ｊ＝７．５Ｈｚ，ＡｒＨ），７．６８−７．７５（ｍ，４Ｈ，ＡｒＨ），８．２２（ｓ，２Ｈ）
元素分析（Ｃ_４２Ｈ_３０Ｆ_１２Ｏ_８Ｓ_２）：Ｃ，５２．７４；Ｈ，３．２８；Ｏ，１３．７０；Ｓ，６．５２（実測値）、Ｃ，５２．８３；Ｈ，３．１７；Ｏ，１３．４１；Ｓ，６．７２（理論値）
分解点：２３１℃
以上の分析結果から、合成したものが、化合物１４の構造と矛盾がないことを確認した。

A 100 mL round bottom flask was charged with compound 7 (1887 mg, 3.7 mmol), compound 9 (929 mg, 1.8 mmol), DMF (25 mL), bubbled with argon gas for 30 minutes, and then tris (dibenzylideneacetone) dioxide. Palladium (0) (32.9 mg, 0.036 mmol) and tri (orthotolyl) phosphine (43.9 mg, 0.144 mmol) were added, and the mixture was stirred at 80 ° C. for 4 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid.
This was purified by recycle preparative HPLC (manufactured by Nippon Analytical Industrial Co., Ltd., LC-9104, solvent: THF) to obtain Compound 14 as a pale yellow crystal (yield 340 mg, yield 20.0%).
The analysis results of Compound 14 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.08-2.37 (m, 8H, H2, H3 of Tetralin), 3.20-3.334 (m, 8H, —CH 2 CF 3) , 6.09-6.6.21 (m, 4H, H1, H4 of Tetralin), 7.40-7.47 (m, 2H, ArH), 7.60 (d, 2H, J = 7.5 Hz) , ArH), 7.68-7.75 (m, 4H, ArH), 8.22 (s, 2H)
Elemental analysis _{(C 42 H 30 F 12 O} 8 S 2): C, 52.74; H, 3.28; O, 13.70; S, 6.52 ( Found), C, 52.83; H 3.17; O, 13.41; S, 6.72 (theoretical value)
Decomposition point: 231 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 14.

Synthesis of compound 15

１００ｍＬの丸底フラスコに、化合物５（１０２０ｍｇ，２．１ｍｍｏｌ）、化合物１０（４９２ｍｇ，１．０ｍｍｏｌ）、ＤＭＦ／トルエン（２５ｍＬ）を入れ、アルゴンガスを３０分間バブリングした後、トリス（ジベンジリデンアセトン）ジパラジウム（０）（３２．９ｍｇ，０．０３６ｍｍｏｌ）、トリ（オルトトリル）ホスフィン（４３．９ｍｇ，０．１４４ｍｍｏｌ）を加え、アルゴン雰囲気下８０℃で１２時間攪拌した。反応溶液をクロロホルムで希釈し、セライト濾過で不溶物を除去し、濾液に水を加え、有機層を分離した。水層はクロロホルムで抽出を行なった。合わせた有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させ、濾液を濃縮し、黄色の固体を得た。これをカラムクロマトグラフィー（固定層：（中性シリカゲル（関東化学製）＋１０ｗｔ％フッ化カリウム，溶媒：ジクロロメタン／酢酸エチル（３／１，ｖ／ｖ）＋２％トリエチルアミン添加）にて精製することにより、黄色の固体を得た。
続けてリサイクル分取ＨＰＬＣ（日本分析工業社製，ＬＣ−９１０４，溶媒：ＴＨＦ）にて精製することにより、淡黄色の結晶として化合物１５を得た（収量２１０ｍｇ，収率４２．７％）
以下に化合物１５の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：０．８５−０．９１（ｍ，１２Ｈ），１．２９−１．３３（ｍ，１６Ｈ），１．６３−１．６９（ｍ，８Ｈ），１．９９−２．０４（ｍ，４Ｈ），２．３２−２．３７（ｍ，１２Ｈ），６．１５（ｄ，４Ｈ，Ｊ＝１８．９Ｈｚ），７．４６（ｄ，２Ｈ，Ｊ＝８．０Ｈｚ），７．６５−７．６９（ｍ，６Ｈ），７．９５（ｄ，２Ｈ，Ｊ＝８．０Ｈｚ），８．１１（ｄ，２Ｈ，Ｊ＝１．２Ｈｚ）
元素分析（Ｃ_５８Ｈ_６８Ｏ_８Ｓ_２）：Ｃ，７２．５０；Ｈ，７．４３；Ｏ，１３．５７；Ｓ，６．４９（実測値）、Ｃ，７２．７７；Ｈ，７．１６；Ｏ，１３．３７；Ｓ，６．７０（理論値）
融点：１７９．０℃
以上の分析結果から、合成したものが、化合物１５の構造と矛盾がないことを確認した。

A 100 mL round bottom flask was charged with compound 5 (1020 mg, 2.1 mmol), compound 10 (492 mg, 1.0 mmol), DMF / toluene (25 mL), bubbled with argon gas for 30 minutes, and tris (dibenzylideneacetone). ) Dipalladium (0) (32.9 mg, 0.036 mmol) and tri (orthotolyl) phosphine (43.9 mg, 0.144 mmol) were added, and the mixture was stirred at 80 ° C. for 12 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. This was purified by column chromatography (fixed layer: (neutral silica gel (manufactured by Kanto Chemical) + 10 wt% potassium fluoride, solvent: dichloromethane / ethyl acetate (3/1, v / v) + 2% triethylamine added)). A yellow solid was obtained.
Subsequently, it was purified by recycle preparative HPLC (manufactured by Nippon Analytical Industrial Co., Ltd., LC-9104, solvent: THF) to obtain Compound 15 as light yellow crystals (yield 210 mg, yield 42.7%).
The analysis results of Compound 15 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.85-0.91 (m, 12H), 1.29-1.33 (m, 16H), 1.63-1.69 (m, 8H), 1.99-2.04 (m, 4H), 2.32-2.37 (m, 12H), 6.15 (d, 4H, J = 18.9 Hz), 7.46 (d, 2H, J = 8.0 Hz), 7.65-7.69 (m, 6H), 7.95 (d, 2H, J = 8.0 Hz), 8.11 (d, 2H, J = 1.2 Hz) )
Elemental analysis _{(C 58 H 68 O 8 S} 2): C, 72.50; H, 7.43; O, 13.57; S, 6.49 ( Found), C, 72.77; H, 7 .16; O, 13.37; S, 6.70 (theoretical value)
Melting point: 179.0 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 15.

Synthesis of compound 16

１００ｍＬの丸底フラスコに、化合物７（１０２０ｍｇ，２．１ｍｍｏｌ）、化合物１０（４９２ｍｇ，１．０ｍｍｏｌ）、ＤＭＦ／トルエン（２５ｍＬ）を入れ、アルゴンガスを３０分間バブリングした後、トリス（ジベンジリデンアセトン）ジパラジウム（０）（１８．３ｍｇ，０．０２ｍｍｏｌ）、トリ（オルトトリル）ホスフィン（２４．４ｍｇ，０．０８ｍｍｏｌ）を加え、アルゴン雰囲気下８０℃で８時間攪拌した。反応溶液をクロロホルムで希釈し、セライト濾過で不溶物を除去し、濾液に水を加え、有機層を分離した。水層はクロロホルムで抽出を行なった。合わせた有機層を飽和フッ化カリウム水溶液、続けて飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させ、濾液を濃縮し、黄色の固体を得た。これをカラムクロマトグラフィー（固定層：（中性シリカゲル（関東化学製）＋１０ｗｔ％フッ化カリウム，溶媒：ジクロロメタン／酢酸エチル（３／１，ｖ／ｖ）＋２％トリエチルアミン添加）にて精製することにより、黄色の固体を得た。
続けて、リサイクル分取ＨＰＬＣ（日本分析工業社製，ＬＣ−９１０４，溶媒：ＴＨＦ）にて精製することにより、淡黄色の結晶として化合物１６を得た（収量１８０ｍｇ，収率３６．５％）
以下に化合物１６の分析結果を示す。
^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ，δ）：２．０８−２．３８（ｍ，８Ｈ，Ｈ２，Ｈ３ ｏｆ Ｔｅｔｒａｌｉｎ），３．１９−３．３３（ｍ，８Ｈ，−ＣＨ２ＣＦ３），６．１２−６．２５（ｍ，４Ｈ，Ｈ１，Ｈ４ ｏｆ Ｔｅｔｒａｌｉｎ），７．４８−７．５０（ｍ，２Ｈ，ＡｒＨ），７．６５−７．７３（ｍ，６Ｈ，ＡｒＨ），７．９７（ｄ，２Ｈ，Ｊ＝８．６Ｈｚ，ＡｒＨ），８．１２（ｄ，２Ｈ，Ｊ＝１．２Ｈｚ，ＡｒＨ）
元素分析（Ｃ_４６Ｈ_３２Ｆ_１２Ｏ_８Ｓ_２）：Ｃ，５５．１７；Ｈ，３．４１；Ｏ，１２．９５；Ｓ，６．０７（理論値）、Ｃ，５４．９８；Ｈ，３．２１；Ｏ，１２．７４；Ｓ，６．３８（理論値）
分解点：２１８℃
以上の分析結果から、合成したものが、化合物１６の構造と矛盾がないことを確認した。

A 100 mL round bottom flask was charged with compound 7 (1020 mg, 2.1 mmol), compound 10 (492 mg, 1.0 mmol), DMF / toluene (25 mL), bubbled with argon gas for 30 minutes, and tris (dibenzylideneacetone). ) Dipalladium (0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at 80 ° C. for 8 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added to the filtrate, and the organic layer was separated. The aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated aqueous potassium fluoride, followed by saturated brine, dried over magnesium sulfate, and the filtrate was concentrated to give a yellow solid. This was purified by column chromatography (fixed layer: (neutral silica gel (manufactured by Kanto Chemical) + 10 wt% potassium fluoride, solvent: dichloromethane / ethyl acetate (3/1, v / v) + 2% triethylamine added)). A yellow solid was obtained.
Then, it refine | purified in recycle preparative HPLC (The Nippon Analytical Industrial company make, LC-9104, solvent: THF), and obtained the compound 16 as a pale yellow crystal | crystallization (yield 180 mg, yield 36.5%).
The analysis results of Compound 16 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.08-2.38 (m, 8H, H2, H3 of Tetralin), 3.19-3.33 (m, 8H, —CH 2 CF 3), 6 12-6.25 (m, 4H, H1, H4 of Tetralin), 7.48-7.50 (m, 2H, ArH), 7.65-7.73 (m, 6H, ArH), 7. 97 (d, 2H, J = 8.6 Hz, ArH), 8.12 (d, 2H, J = 1.2 Hz, ArH)
Elemental analysis _{(C 46 H 32 F 12 O} 8 S 2): C, 55.17; H, 3.41; O, 12.95; S, 6.07 ( theoretical value), C, 54.98; H , 3.21; O, 12.74; S, 6.38 (theoretical value)
Decomposition point: 218 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 16.

[Synthesis of Naphthalene Using Substituent Leaving Compound 4]

合成例１で合成した化合物４（１００ｍｇ）を丸底フラスコに入れ、内温１８０℃のまま１時間攪拌した。続けて、フラスコに氷による冷却部を備えたガラス管を置き、フラスコ内を減圧（４０ｍｍＨｇ）し、内温８０℃のまま加熱を続けることにより昇華精製を行ない、ガラス管に付着した無色の結晶を掻き取った（収量５１．５ｍｇ，収率９９．８％）
この結晶の下記に示す分析を行なったところ
^１Ｈ ＮＭＲ（５００ＭＨｚ、ＣＤＣｌ_３、ＴＭＳ，δ）：７．４８（ｄ，４Ｈ，Ｊ_１＝６．８Ｈｚ），７．８４（ｄ，４Ｈ、Ｊ_１＝８．３Ｈｚ）
元素分析値（Ｃ_１０Ｈ_８）：Ｃ，９３．４６；Ｈ，６．４４（実測値）Ｃ，９３．７１；Ｈ，６．２９（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝１２８（Ｍ＋）
融点：７９．０−８０．０℃
化合物純度（ＬＣ−ＭＳ）：≧９９．９％
以上の結果から、上記反応で得られた無色の結晶がナフタレンであることが確認された。

Compound 4 (100 mg) synthesized in Synthesis Example 1 was placed in a round bottom flask and stirred for 1 hour while maintaining the internal temperature at 180 ° C. Subsequently, a glass tube equipped with a cooling part with ice is placed on the flask, the inside of the flask is depressurized (40 mmHg), and sublimation purification is performed by continuing the heating at an internal temperature of 80 ° C., and colorless crystals attached to the glass tube Was scraped off (yield 51.5 mg, yield 99.8%)
The following analysis of this crystal was performed.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 7.48 (d, 4H, J ₁ = 6.8 Hz), 7.84 (d, 4H, J ₁ = 8.3 Hz)
Elemental analysis value (C ₁₀ H ₈ ): C, 93.46; H, 6.44 (actual value) C, 93.71; H, 6.29 (theoretical value)
Mass spectrometry: GC-MS m / z = 128 (M +)
Melting point: 79.0-80.0 ° C
Compound purity (LC-MS): ≧ 99.9%
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were naphthalene.

[Synthesis 1 of 2-iodonaphthalene Using Substituent Leaving Compound 5]

合成例１で合成した化合物５（９７．２８ｍｇ，０．２ｍｍｏｌ）を丸底フラスコに入れ、内温１８０℃のまま１時間攪拌した。続けて、フラスコに氷による冷却部を備えたガラス管を置き、フラスコ内を減圧（４０ｍｍＨｇ）し、内温５０℃のまま加熱を続けることにより昇華精製を行ない、ガラス管に付着した無色の結晶を掻き取った（収量５０．６６ｍｇ，収率９９．７％）
この結晶の下記に示す分析を行なったところ、
^１Ｈ ＮＭＲ（４００ＭＨｚ，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）
元素分析値（Ｃ_１０Ｈ_７Ｉ）：Ｃ，４７．１１；Ｈ，２．９４（実測値）Ｃ，４７．２７；Ｈ，２．７８（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝２５４（Ｍ＋）
融点：５０．５−５２．０℃
化合物純度（ＬＣ−ＭＳ）：≧９９．８％
以上の結果から、上記反応で得られた無色の結晶が２−ヨードナフタレンであることが確認された。

Compound 5 (97.28 mg, 0.2 mmol) synthesized in Synthesis Example 1 was placed in a round bottom flask and stirred for 1 hour while maintaining the internal temperature at 180 ° C. Subsequently, a glass tube equipped with a cooling part with ice is placed in the flask, the inside of the flask is depressurized (40 mmHg), and sublimation purification is performed by continuing the heating at an internal temperature of 50 ° C., and colorless crystals attached to the glass tube Was scraped off (yield 50.66 mg, yield 99.7%)
When the following analysis of this crystal was performed,
¹ H NMR (400 MHz, CDCl ₃ , TMS, δ): 7.46-7.52 (m, 2H) 7.55-7.58 (m, 1H), 7.68-7.74 (m, 2H) ), 7.76-7.82 (m, 1H), 8.22-8.26 (m, 1H)
Elemental analysis (C ₁₀ H ₇ I): C, 47.11; H, 2.94 (actual measurement) C, 47.27; H, 2.78 (theoretical value)
Mass spectrometry: GC-MS m / z = 254 (M +)
Melting point: 50.5-52.0 ° C
Compound purity (LC-MS): ≧ 99.8%
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were 2-iodonaphthalene.

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

[Synthesis of 2-iodonaphthalene using Substituent Leaving Compound 7]
The reaction was performed in the same manner except that the compound 6 used in Example 2 was replaced with the compound 7 (102.0 mg, 0.2 mmol) and the internal temperature of the flask was changed to 160 ° C.
Colorless crystals adhering to the glass tube were scraped off (yield 50.76 mg, yield 99.9%).
When the following analysis of this crystal was performed, the same analysis results as in Example 2 were obtained.
From the above results, it was confirmed that the colorless crystals obtained by the above reaction were 2-iodonaphthalene.

  From Examples 1 to 4, it was shown that naphthalene and derivatives thereof were quantitatively obtained at a relatively low temperature of 180 ° C. or lower and a high yield of 99% or higher using a substituent-eliminating compound. It was also shown that the reaction was completed at a lower temperature in a compound having an alkyl group with high electron-withdrawing properties such as partially halogenated (fluorinated).

[Synthesis 1 of Organic Semiconductor Compound 1 (Compound 17)]

合成例３で合成した化合物１１（２００ｍｇ、０．２３ｍｍｏｌ）を丸底フラスコに入れ、アルゴン雰囲気下、２４５℃（フラスコ内温）で１時間加熱攪拌を行なった。
得られた固体をトルエン、続けてメタノールで洗浄し、真空下乾燥することで黄色の結晶として化合物１７を得た。（収量８６．９ｍｇ、収率９６．３％）
化合物１７の分析結果を以下に示す。
元素分析値（Ｃ_２６Ｈ_１６Ｓ_２）：Ｃ，７９．８４；Ｈ，４．００；Ｓ，１６．１０（実測値）Ｃ，７９．５５；Ｈ，４．１１；Ｓ，１６．３４（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝３９２（Ｍ＋）
融点：３５７．７℃
化合物純度（ＧＣＭＳ）：≧９９．８％
以上の分析結果から、合成したものが、化合物１７の構造と矛盾がないことを確認した。

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

[Synthesis 2 of Organic Semiconductor Compound 1 (Compound 17)]

実施例５で用いた化合物１１を化合物１２（１８４．２ｍｇ、０．２３ｍｍｏｌ）に換え、反応温度を２７０℃に変えた以外は実施例５と同様に反応および精製を行なった。
同様に黄色の結晶として化合物１７を得た。（収量８６．３ｍｇ、収率９６．３％）
本反応で得られた化合物１７の分析結果を以下に示す。
元素分析値（Ｃ_２６Ｈ_１６Ｓ_２）：Ｃ，７９．６４；Ｈ，４．１０；Ｓ，１６．２０（実測値）Ｃ，７９．５５；Ｈ，４．１１；Ｓ，１６．３４（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝３９２（Ｍ＋）
融点：３５７．２℃
化合物純度（ＧＣＭＳ）：≧９９．７％
以上の分析結果から、合成したものが、化合物１７の構造と矛盾がないことを確認した。

The reaction and purification were performed in the same manner as in Example 5 except that the compound 11 used in Example 5 was changed to the compound 12 (184.2 mg, 0.23 mmol) and the reaction temperature was changed to 270 ° C.
Similarly, Compound 17 was obtained as yellow crystals. (Yield 86.3 mg, Yield 96.3%)
The analysis results of Compound 17 obtained by this reaction are shown below.
Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.64; H, 4.10; S, 16.20 (actual value) C, 79.55; H, 4.11; S, 16.34 (Theoretical value)
Mass spectrometry: GC-MS m / z = 392 (M +)
Melting point: 357.2 ° C
Compound purity (GCMS): ≧ 99.7%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 17.

[Synthesis 3 of Organic Semiconductor Compound 1 (Compound 17)]

実施例５で用いた化合物１１を化合物１３（２１９．６ｍｇ、０．２３ｍｍｏｌ）に換え、反応温度を２００℃に変えた以外は実施例５と同様に反応および精製を行なった。
同様に黄色の結晶として化合物１７を得た。（収量８９．２ｍｇ、収率９８．８％）
本反応で得られた化合物１７の分析結果を以下に示す。
元素分析値（Ｃ_２６Ｈ_１６Ｓ_２）：Ｃ，７９．５８；Ｈ，４．１１；Ｓ，１６．３２（実測値）Ｃ，７９．５５；Ｈ，４．１１；Ｓ，１６．３４（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝３９２（Ｍ＋）
融点：３５７．２℃
化合物純度（ＧＣＭＳ）：≧９９．７％
以上の分析結果から、合成したものが、化合物１７の構造と矛盾がないことを確認した。

The reaction and purification were carried out in the same manner as in Example 5 except that the compound 11 used in Example 5 was replaced with the compound 13 (219.6 mg, 0.23 mmol) and the reaction temperature was changed to 200 ° C.
Similarly, Compound 17 was obtained as yellow crystals. (Yield 89.2 mg, Yield 98.8%)
The analysis results of Compound 17 obtained by this reaction are shown below.
Elemental analysis (C ₂₆ H ₁₆ S ₂ ): C, 79.58; H, 4.11; S, 16.32 (actual measurement) C, 79.55; H, 4.11; S, 16.34 (Theoretical value)
Mass spectrometry: GC-MS m / z = 392 (M +)
Melting point: 357.2 ° C
Compound purity (GCMS): ≧ 99.7%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 17.

[Synthesis of Organic Semiconductor Compound 2 (Compound 18)]

実施例５で用いた化合物１１を化合物１４（２０８．１ｍｇ、０．２３ｍｍｏｌ）に換え、反応温度を２４０℃に変えた以外は実施例５と同様に反応を行ない、得られた固体をクロロホルム、アセトン、メタノールで洗浄し真空下で乾燥することで、黄緑色の結晶として化合物１８を得た。（収量１００ｍｇ、収率９８．３％）
本反応で得られた化合物１８の分析結果を以下に示す。
元素分析値（Ｃ_３０Ｈ_１８Ｓ_２）：Ｃ，８１．２１；Ｈ，４．１０；Ｓ，１４．５９（実測値）Ｃ，８１．４１；Ｈ，４．１０；Ｓ，１４．４９（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝４４２（Ｍ＋）
融点：４３８．２℃
化合物純度（ＧＣＭＳ）：≧９９．８％
以上の分析結果から、合成したものが、化合物１８の構造と矛盾がないことを確認した。

Compound 11 used in Example 5 was replaced with Compound 14 (208.1 mg, 0.23 mmol), and the reaction was carried out in the same manner as in Example 5 except that the reaction temperature was changed to 240 ° C. The resulting solid was treated with chloroform, The compound 18 was obtained as yellowish green crystals by washing with acetone and methanol and drying under vacuum. (Yield 100 mg, yield 98.3%)
The analysis results of Compound 18 obtained by this reaction are shown below.
Elemental analysis _{(C 30 H 18 S 2)} : C, 81.21; H, 4.10; S, 14.59 ( Found) C, 81.41; H, 4.10 ; S, 14.49 (Theoretical value)
Mass spectrometry: GC-MS m / z = 442 (M +)
Melting point: 438.2 ° C
Compound purity (GCMS): ≧ 99.8%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 18.

[Synthesis 1 of Organic Semiconductor Compound 3 (Compound 19)]

実施例５で用いた化合物１１を化合物１５（２０８．１ｍｇ、０．２３ｍｍｏｌ）に換え、反応温度を２５５℃に変えた以外は実施例５と同様に反応を行ない、クロロホルム、メタノールで洗浄し真空下で乾燥することで、淡黄色の結晶として化合物１９を得た。（収量１１０ｍｇ、収率９７．１％）
本反応で得られた化合物１９の分析結果を以下に示す。
元素分析値（Ｃ_３４Ｈ_２０Ｓ_２）：Ｃ，８２．６７；Ｈ，４．１０；Ｓ，１３．１４（実測値）Ｃ，８２．８９；Ｈ，４．０９；Ｓ，１３．０２（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝４９２（Ｍ＋）
融点：３７８．２℃
化合物純度（ＧＣＭＳ）：≧９９．５％
以上の分析結果から、合成したものが、化合物１９の構造と矛盾がないことを確認した。

Compound 11 used in Example 5 was replaced with Compound 15 (208.1 mg, 0.23 mmol), and the reaction was carried out in the same manner as in Example 5 except that the reaction temperature was changed to 255 ° C., washed with chloroform and methanol, and vacuumed The compound 19 was obtained as a pale yellow crystal | crystallization by drying under. (Yield 110 mg, Yield 97.1%)
The analysis results of Compound 19 obtained by this reaction are shown below.
Elemental analysis _{(C 34 H 20 S 2)} : C, 82.67; H, 4.10; S, 13.14 ( Found) C, 82.89; H, 4.09 ; S, 13.02 (Theoretical value)
Mass spectrometry: GC-MS m / z = 492 (M +)
Melting point: 378.2 ° C
Compound purity (GCMS): ≧ 99.5%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 19.

[Synthesis 2 of Organic Semiconductor Compound 3 (Compound 19)]

実施例５で用いた化合物１１を化合物１６（２０８．１ｍｇ、０．２３ｍｍｏｌ）に換え、反応温度を２２０℃に変えた以外は実施例５と同様に反応を行ない、クロロホルム、アセトン、メタノールで洗浄し真空下で乾燥することで、淡黄色の結晶として化合物１９を得た。（収量１１１．８ｍｇ、収率９８．７％）
本反応で得られた化合物１９の分析結果を以下に示す。
元素分析値（Ｃ_３４Ｈ_２０Ｓ_２）：Ｃ，８２．５２；Ｈ，４．０８；Ｓ，１３．１７（実測値）Ｃ，８２．８９；Ｈ，４．０９；Ｓ，１３．０２（理論値）
質量分析：ＧＣ−ＭＳ ｍ／ｚ＝４９２（Ｍ＋）
融点：３７７．９℃
化合物純度（ＧＣＭＳ）：≧９９．４％
以上の分析結果から、合成したものが、化合物１９の構造と矛盾がないことを確認した。

The reaction was conducted in the same manner as in Example 5 except that the compound 11 used in Example 5 was changed to the compound 16 (208.1 mg, 0.23 mmol) and the reaction temperature was changed to 220 ° C., and washed with chloroform, acetone and methanol. The compound 19 was obtained as light yellow crystals by drying under vacuum. (Yield 111.8 mg, Yield 98.7%)
The analysis results of Compound 19 obtained by this reaction are shown below.
Elemental analysis _{(C 34 H 20 S 2)} : C, 82.52; H, 4.08; S, 13.17 ( Found) C, 82.89; H, 4.09 ; S, 13.02 (Theoretical value)
Mass spectrometry: GC-MS m / z = 492 (M +)
Melting point: 377.9 ° C
Compound purity (GCMS): ≧ 99.4%
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 19.

From the results of Example 10 to 15 which will be described later, a highly soluble π electron conjugated compound having a high yield of 97% or more and a high purity of 99% or more is obtained only by heating and washing operations at about 200 to 250 ° C. It was shown that it is possible to obtain in
It was also found that the temperature required for the conversion was approximately below the sublimation temperature of each compound (defined as 1% weight loss temperature). For example, after the weight loss that occurs during the conversion in FIG. 2 is completed, a region where the graph is almost horizontal is seen from 300 ° C. to 340 ° C., and a weight loss of 1% or more starts at a higher temperature. I can think of you.
This suggests that this is an effective method not only for producing low-molecular-weight organic solvents such as naphthalene but also for π-electron conjugated compounds that are inherently poorly soluble in organic solvents.
They can also be applied to pigments, organic semiconductor molecules, and many other molecules.

[Evaluation of solubility]
Compounds 11 to 19 synthesized in Synthesis Example 3 were respectively added to toluene, THF, anisole, and chloroform (2.0 mg each) until they remained undissolved, stirred under solvent reflux for 10 minutes, cooled to room temperature, and further added 1 After stirring for 16 hours and allowing to stand for 16 hours, the supernatant was filtered through a 0.2 μm PTFE filter to obtain a saturated solution. This was dried under reduced pressure to calculate the solubility of the precursor in each solvent. The results are shown in Table 1.

（表１においては◎とは溶解度が０．５ｗｔ％以上であり、○とは０．１ｗｔ％以上０．５ｗｔ％未満、△は０．００５ｗｔ％以上０．１ｗｔ％未満、×は０．００５ｗｔ％未満であったことを示す。）
化合物１１乃至１６を用いたいずれの場合においても、溶媒還流下で前駆体化合物が脱離した化合物（即ち化合物１７乃至１９）の存在は認められなかった。

(In Table 1, ◎ means a solubility of 0.5 wt% or more, ○ means 0.1 wt% or more and less than 0.5 wt%, Δ means 0.005 wt% or more and less than 0.1 wt%, × means 0.005 wt% (It indicates that it was less than%.)
In any case where the compounds 11 to 16 were used, the presence of the compound from which the precursor compound was eliminated under solvent reflux (that is, the compounds 17 to 19) was not observed.

From Table 1, it was found that the solvent has a solubility of approximately 0.1 wt% or more with respect to many solvents having different polarities, and it is clear that the selectivity of the solvent in the coating process is rich.
In addition, the compounds 17, 18 and 19 which are the materials after conversion are soluble in 0.005 wt% or less in all these solvents, suggesting that the compounds converted by the elimination reaction are insolubilized.
Further, it was found that in the solution state, at least under anisole reflux conditions (154 ° C.), it has thermal stability and storage stability that are not decomposed.
Although it is not certain, desorption occurs easily when the distance between each molecule is very close as in the solid state, but desorption does not easily occur when there is a certain distance between molecules as in the solution. It can be considered.

[Observation Example of Desorption Behavior of Compound 11]
Compound 11 (5 mg) synthesized in Synthesis Example 3 was heated for 30 minutes on a hot plate set at an arbitrary temperature (150, 160, 170, 180, 220, 230, 240, 260 ° C.) through a silicon wafer. The sample was adjusted.
IR spectra (KBr method, Spectrum GX (trade name), manufactured by Perkin Elmer) of the sample, compound 11 before heating, and compound 17 after conversion were measured. The result is shown in FIG.
Under the heating condition of Compound 11 at 240 ° C., the absorption of —O— (1156 cm ⁻¹ and C═O (1726 cm ⁻¹ )) disappears and the presence of new absorption (810, 738, 478 cm ⁻¹ , aromatic) Was confirmed. This is consistent with the spectrum of compound 17.
Further, the thermal decomposition behavior of Compound 11 was measured at 25 ° C. to 500 ° C. using TG-DTA (reference Al ₂ O ₃ , under a nitrogen stream (200 mL / min), EXSTAR 6000 (trade name), manufactured by Seiko Instruments Inc.). The range was heated at a rate of 5 ° C./min and observed. The result is shown in FIG.
In TG-DTA, a weight loss of 56.7% was observed from 160 to 290 ° C. This is almost consistent with 4 molecules of caproic acid (theoretical value: 54.2%). The presence of a melting point was observed at 357.7 ° C. This is consistent with the value of compound 17.
From the above results, it was shown that compound 11 was converted to compound 17 by heating.
It was also shown that the threshold for elimination reaction is around 240 ° C.

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

[Observation Example of Desorption Behavior of Compound 15]
A sample was prepared in the same manner except that the compound 11 of Example 12 was changed to the compound 15 and the heating conditions were 180, 200, 220, 230, 240, 250, 260, and 280 ° C., the IR spectrum was measured, and the IR spectrum was measured. The conversion temperature was measured and estimated. Under the heating condition of Compound 15 at 250 ° C., the absorption of —O— (1156 cm ⁻¹ and C═O (1726 cm ⁻¹ )) disappears, and there is a new absorption (810, 738, 478 cm ⁻¹ , aromatic). Was confirmed. This is consistent with the spectrum of compound 19. Similarly, TG-DTA was measured. In TG-DTA, a weight loss of 50.7% was observed from 200 to 300 ° C. This is almost consistent with 4 molecules of caproic acid (theoretical value 48.5%). The presence of a melting point was observed at 358.2 ° C. This is consistent with the value of compound 19.
From the above results, it was shown that Compound 15 was converted to Compound 19 by heating.
It was also shown that the threshold for elimination reaction is around 250 ° C.

From the above examples, the desorption behavior and the threshold temperature of the desorption reaction could be estimated. In addition, the effect of the combined π-conjugated core was not so great, and it was shown that the temperature at which the elimination reaction changes due to the difference in the alkyl chain introduced into the ester moiety. In the case of the compound in the present invention, it was shown that the target π-conjugated compound can be obtained by heating at about 250 ° C.
In Examples 12 to 14, the measured weight loss is larger than the theoretical value because the compounds 17 and 19 are relatively high in sublimation because of high temperature and under a nitrogen stream. This is presumably because the crystal contains a solvent.

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

[Comparative Example 1]
As Comparative Example 1, the solution was prepared in the same manner except that the compounds 11, 14, and 15 of Example 15 were changed to the compounds 17, 18, and 19 and dichlorobenzene heated to 150 ° C. was used instead of THF. Fabrication was performed.
In any of the films, crystals were deposited to the extent that they were visually confirmed, and it was confirmed that the films were discontinuous. Even in the polarization microscope, a plurality of discontinuous and colored domains were observed. When confirmed with a scanning probe microscope, a surface roughness of 100 μm or more was observed.

  From the above results, it was shown that the production method of the present invention is effective in thinning a poorly soluble compound that slightly dissolves in some high-boiling solvents.

[Production and evaluation of organic thin-film transistors by solution process]
Thin films containing compound 11 were prepared in the same manner as in Example 15. The thin film was subjected to an annealing treatment at 250 ° C. for 30 minutes in an argon atmosphere to convert the thin film into a thin film (film thickness 50 nm) made of the organic semiconductor compound 1.
By using a shadow mask on the thin film, gold is vacuum-deposited (back pressure: 10 ⁻⁴ Pa, deposition rate: 1-2 Å / s, film thickness: 50 nm) to form source and drain electrodes (channel length 50 μm, channel width 2 mm) ) To produce 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. 5 shows an IV characteristic diagram of this FET element. In FIG. 5, the white circle is the left vertical axis (the absolute value of the drain current, the black circle is the right 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 formula | equation was used for calculation of the field effect mobility of an organic thin-film transistor.
Ids = μCinW (Vg−Vth) 2 / 2L
(Where Cin is the capacitance per unit area of the gate insulating film, W is the channel width, L is the channel length, Vg is the gate voltage, Ids is the source / drain current, μ is the mobility, and Vth is the gate that the channel begins to form. (It is the threshold voltage.)
Further, the ratio of the on current at 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.

  In Example 16, an FET element was prepared in the same manner as in Example 16 except that the compound 14 was used instead of the compound 11 and the thin film was formed of the organic semiconductor compound 2, and the characteristics were evaluated. The results are shown in Table 2.

  In Example 16, an FET element was prepared in the same manner as in Example 16 except that the compound 15 was used instead of the compound 11 and the thin film was formed of the organic semiconductor compound 3, and the characteristics were evaluated. The results are shown in Table 2.

[Comparative Example 2]
Using the dichlorobenzene solution described in Comparative Example 1, a thin film made of the organic semiconductor compound 1 was formed on the same substrate as in Example 16, to produce an FET element, and the characteristics were evaluated. The results are shown in Table 2.

[Comparative Example 3]
Using the dichlorobenzene solution described in Comparative Example 1, a thin film made of the organic semiconductor compound 3 was formed on the same substrate as in Example 16, to produce an FET element, and the characteristics were evaluated. The results are shown in Table 2.

[Comparative Example 4]
Using the dichlorobenzene solution described in Comparative Example 1, a thin film made of the organic semiconductor compound 3 was formed on the same substrate as in Example 16, to produce an FET element, and the characteristics were evaluated. The results are shown in Table 2.

  From the above examples, only by forming a film by dissolving a poorly soluble organic semiconductor compound in a high-boiling solvent, good FET characteristics cannot be obtained, but using the substituent-elimination compound of the present invention, It has been clarified that by converting to a film containing an organic semiconductor compound, good FET characteristics can be obtained even by using a solution process. All of the organic thin film transistors of the present invention showed excellent hole mobility and current on / off ratio, and it was revealed that they have excellent characteristics as organic thin film transistors. From this, it was shown that the substituent-elimination compound of the present invention and the organic semiconductor compound obtained thereby are useful in the production of an organic electronic device element such as an organic thin film transistor.

The substituent-eliminating compound of the present invention has excellent solubility in various organic solvents, and uses a desorption reaction by application of energy to produce a high yield of a specific compound, organic semiconductor compound, etc. without producing a terminal olefin. Since it is possible to synthesize at a high rate, the process ability is excellent.
Moreover, even if it is an organic semiconductor compound that is difficult to form due to poor solubility, the substituent-elimination compound of the present invention is used as an organic semiconductor compound precursor, and after film formation, heat is added to the organic semiconductor compound. Can be obtained easily, and a continuous organic semiconductor film can be easily obtained, and patterning of the organic semiconductor film is possible by washing and removing unconverted sites. Application of this film to organic electronic devices In particular, for electronic devices such as semiconductors, optical-electronic devices such as EL light emitting elements, thin film solar cells, photoelectric conversion devices such as dye-sensitized solar cells, electronic paper, various sensors, RFIDs (radio frequency identification), etc. There is a possibility of application.

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

Japanese Patent Laid-Open No. 5-05568 WO2006-077788 JP 2007-224019 A JP 2008-270843 A JP 2009-105336 A JP 2009-84555 A JP 2006-352143 A Japanese Patent Application No. 2009-061749

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Claims (4)

Under following general formula (IV), substituted elimination compound which is a partial structure represented by (V).

(In the formula, n is an integer of 2 or more, and the substituents in parentheses may be the same or different. Ar is an aryl group or heteroaryl group which may have a substituent. Here, the general formulas (IV) and (V) represent that Ar is bonded to the cyclohexene derivative skeleton via a covalent bond or condensed, and X ₁ and X ₂ are substituted or unsubstituted. Represents an acyloxy group having 1 or more carbon atoms, Y ₁ and Y ₂ are both hydrogen atoms, X ₁ and X ₂ may be the same or different, and are bonded to each other to form the cyclic acyloxy group; R _{1 to} R _{4 each} represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a cyano group. Wherein Ar 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) a compound in which the rings of (i) are linked via a covalent bond,
The substitution elimination compound according to claim 1 , wherein the substitution elimination compound is at least one compound selected from the group consisting of: The substituent elimination compound according to claim 2 , wherein the aromatic hydrocarbon ring and the aromatic heterocycle are a benzene ring and a thiophene ring. Ar is at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyloxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, and an aryl group. The following structural formula that may have:

The substituted elimination compound according to any one of claims 1 to 3 , wherein

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