JP2013075832A - Method for producing alkoxy thiophene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method, with which an alkoxy thiophene derivative, exhibiting a high conductivity in a doped state and useful as a monomer for a thiophene-based polymer having a high air stability, can be efficiently synthesized, without going through a unstable intermediate.SOLUTION: The alkoxy thiophene derivative is obtained in good yield by a cross coupling reaction of a metal compound or a boron compound of an alkoxy thiophene compound with a halogenated compound of a (hetero)arylene compound having a group composed of a monocyclic, condensed polycyclic or condensed ring thiophene derivative and the like in the presence of a transition metal catalyst.

Description

  The present invention relates to a method for producing an alkoxythiophene derivative. The alkoxythiophene derivative produced by the method of the present invention is useful as a semiconductor or conductive polymer material.

  Obtained by polymerizing a compound having a five-membered or six-membered ring structure in which heteroatoms exist inside or outside the ring, such as pyrrole, thiophene, aniline, or a compound having a hydrocarbon aromatic ring structure. The obtained polymer has semiconducting properties, and its use for various organic devices such as organic electrolytic transistors, thin film transistors, and RFIDs has been studied. In addition, these polymers doped oxidatively and reductively have conductivity, and the electrical and optical properties can be appropriately controlled by adjusting the doping amount. Applications to various organic materials such as chromic materials, various sensors, primary batteries, secondary batteries, solid electrolytic capacitors and antistatic agents are being studied.

  For example, Patent Document 1 describes that a polymer doped with a copolymer containing alkylthiophene and thieno [3,2-b] thiophene has conductivity. However, specific conductivity and stability are not mentioned, and Non-Patent Document 1 reports that the conductivity of these polymers is significantly reduced by exposure to the atmosphere. Further, it has been reported that a copolymer containing alkylthiophene and dithieno [3,2-b: 2 ′, 3′-d] pyrrole exhibits high conductivity when oxidatively doped. The electrical conductivity is greatly reduced by exposure to the atmosphere (Non-patent Document 2).

  Accordingly, there is a need to provide a polymer that exhibits higher conductivity and is stable even in the air and a method for producing the same.

  The present inventors have found that the above problem can be solved by the following method (Japanese Patent Application No. 2011-121312). That is, by using an alkoxythiophene derivative containing an alkoxy group as a monomer, a polymer that exhibits semiconductor performance and high conductivity in a doped state, and that has atmospheric stability without decreasing conductivity due to atmospheric exposure. Can be provided.

  However, according to the production method described in Japanese Patent Application No. 2011-121312, an alkoxythiophene derivative which is a polymerization precursor is synthesized by reacting 3-alkoxy-2-halogenothiophene with a trialkyltin compound in the presence of a catalyst. However, an alkoxythiophene derivative cannot be obtained in a high yield. This is because the alkoxy group which is an electron donating group is bonded to the 3-position of 2-halogenothiophene, which adversely affects the oxidative addition of the catalyst, the target reaction is difficult to proceed, and the yield is low. Conceivable. Moreover, 3-alkoxy-2-halogenothiophene is known to polymerize easily (Non-Patent Document 3), and is difficult to handle due to poor stability.

Advanced Functional Materials, 19, 1906 (2009) Journal of American Chemical Society, 130, 13167 (2008) Australian Journal of Chemistry, 64, 335 (2011)

Special table 2008-504379

  Therefore, an object of the present invention is to provide a production method capable of efficiently synthesizing an alkoxythiophene derivative without going through an unstable intermediate.

  The present inventors have made further intensive studies and found that the above object can be achieved by carrying out a reaction using an alkoxythiophene compound and a halogenated heteroarylene compound, and have reached the present invention.

That is, the present invention
1. The following chemical formula (1)

〔化学式（１）中、Ｒ^１は下記化学式（２）
Ｒ^３−〔Ｗ−（ＣＨ_２）_ａ〕_ｂ− ・・・（２）
（式（２）中、Ｒ^３は水素原子、又は置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基であり、Ｗは酸素原子又は硫黄原子であり、〔Ｗ−（ＣＨ_２）_ａ〕は繰り返し単位毎にＷとａとが同一又は異なっていてもよく、ａは１〜２０、ｂは０〜２０の正数である）で示される側鎖であり、
Ｒ^２は水素原子、置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状、若しくは環状のアルキル基又はアルコキシ基であり、
Ｍはハロゲン化マグネシウム、ハロゲン化亜鉛、トリアルキル化スズ、ホウ酸又はホウ酸エステルである〕
で示されるアルコキシチオフェン化合物と、下記化学式（３）
Ｘ^１−Ａ−Ｘ^２ ・・・（３）
〔化学式（３）中、Ａは置換基を有していてもよい２価のヘテロアリーレン基であり、Ｘ^１及びＸ^２はそれぞれ同一又は異なるハロゲン原子である〕
で示されるヘテロアリーレン化合物とを反応させることを特徴とする、下記化学式（４）

[In the chemical formula (1), R ¹ represents the following chemical formula (2)
R ^3- [W— (CH ₂ ) _a ] _b − (2)
(In Formula (2), R ³ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and W is an oxygen atom or a sulfur atom. And [W— (CH ₂ ) _a ] may be the same or different for W and a for each repeating unit, where a is 1 to 20 and b is a positive number from 0 to 20. Side chain,
R ² is a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms,
M is magnesium halide, zinc halide, trialkylated tin, boric acid or borate ester)
And an alkoxythiophene compound represented by the following chemical formula (3)
X ¹ -A-X ² (3)
[In Formula (3), A is a divalent heteroarylene group which may have a substituent, and X ¹ and X ² are the same or different halogen atoms, respectively]
A heteroarylene compound represented by the following formula (4) is reacted:

〔化学式（４）中、Ｒ^１及びＲ^２は前記と同じである〕
で示されるアルコキシチオフェン誘導体の製造方法；
２．置換基を有していてもよい２価のヘテロアリーレン基がチオフェン誘導体からなる基である、上記１に記載のアルコキシチオフェン誘導体の製造方法；
３．置換基を有していてもよい２価のヘテロアリーレン基が下記化学式（５）〜（９）から選択されるいずれかである、上記２に記載のアルコキシチオフェン誘導体の製造方法

[In the chemical formula (4), R ¹ and R ² are the same as above]
A process for producing an alkoxythiophene derivative represented by:
2. The method for producing an alkoxythiophene derivative according to the above 1, wherein the divalent heteroarylene group which may have a substituent is a group comprising a thiophene derivative;
3. 3. The method for producing an alkoxythiophene derivative according to 2 above, wherein the divalent heteroarylene group which may have a substituent is any one selected from the following chemical formulas (5) to (9):

〔化学式（５）〜（９）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１，Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７はそれぞれ同一または異なって水素原子、置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状、若しくは環状のアルキル基又はアルコキシ基であり、Ｒ^１８は、水素原子、置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状、若しくは環状のアルキル基、アルコキシ基、アリール基又はヘテロアリール基である〕；
である。

[In the chemical formulas (5) to (9), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ is the same or different and is a hydrogen atom, a linear, branched, or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms that may have a substituent, and R ¹⁸ is a hydrogen atom. A C1-C20 linear, branched or cyclic alkyl group, alkoxy group, aryl group or heteroaryl group which may have a substituent];
It is.

  By using the production method of the present invention, an alkoxythiophene derivative can be produced efficiently without going through an unstable intermediate. The alkoxythiophene derivative thus obtained is useful as a polymer material that exhibits high conductivity in a doped state and has atmospheric stability.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

As shown in the chemical formula (1), the alkoxythiophene compound used in the production method of the present invention includes magnesium halide, zinc halide, trialkylated tin, boric acid represented by M at the 2-position of the thiophene ring. And having any functional group selected from borate esters and having an alkoxy group represented by —O—R ¹ at the 3-position of the thiophene ring.

In the chemical formula (2) representing R ¹ in the chemical formula (1), the repeating unit of [W— (CH ₂ ) _a ] may be such that W is only an oxygen atom or only a sulfur atom, and both atoms are ordered. It may be contained regularly or irregularly.

In the chemical formula (2), examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ³ include a methyl group, ethyl group, n-propyl group, n-butyl group, n- Pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, isopropyl group, isobutyl group, sec-butyl group, 2-methylhexyl group, 2-ethylhexyl group, Examples include a cyclohexyl group and a cyclopropyl group. The alkyl group represented by R ³ may have a substituent, and examples of the substituent include an alkoxy group having 1 to 20 carbon atoms.

In the chemical formula (1), examples of the alkoxy group represented by —O—R ¹ include an octyloxy group, a dodecyloxy group, a 2-methoxyethoxy group, a 2- (2-methoxyethoxy) ethoxy group, and 2- ( 2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (3- (2-methoxyethoxy) propoxy) ethoxy group, 3- (3-methoxypropoxy) propoxy group and the like.

  Examples of the magnesium halide represented by M in the chemical formula (1) include -MgCl, -MgBr, -MgI and the like.

  Examples of the zinc halide represented by M in the chemical formula (1) include -ZnCl, -ZnBr, and -ZnI.

Examples of the trialkyltin represented by M in the chemical formula (1) include —Sn (Me) ₃ and —Sn (Bu) ₃ .

Examples of the boric acid ester represented by M in the chemical formula (1) include -B (OMe) ₂ , -B (OEt) ₂ , -B (OPr) ₂ , -B (OBu) ₂ , and chemical formulas (10) to (13). And cyclic borate esters represented by the formula:

In the chemical formula (1), examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ² include a methyl group, ethyl group, n-propyl group, n-butyl group, n- Pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, isopropyl group, isobutyl group, sec-butyl group, 2-methylhexyl group, 2-ethylhexyl group, Examples include a cyclohexyl group and a cyclopropyl group.

In the chemical formula (1), examples of the alkoxy group represented by R ² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, n-hexyloxy group, isohexyloxy group, 2-ethylhexyloxy group, n-heptyloxy group, n-octyloxy group , N-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyltetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyl An oxy group, n-nonadecyloxy group, n-icosyloxy group, etc. are mentioned. .

  These alkyl groups and alkoxy groups may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkyleneoxy having 1 to 20 carbon atoms. Group, halogen atom and the like.

  The heteroarylene compound used in the production method of the present invention has the same or different halogen atoms at both ends as shown by the chemical formula (3), and has a substituent represented by A between them. It may have a divalent heteroarylene group.

In the chemical formula (3), examples of the halogen atom represented by X ¹ and X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the chemical formula (3), examples of the divalent heteroarylene group represented by A include pyridine-2,5-diyl, pyrimidine-2,5-diyl, thiophene-2,5-diyl, selenophene-2,5-diyl, 2,2'-bithiophene-5,5'-diyl, thieno [3,2-b] thiophene-2,5-diyl, thieno [2,3-b] thiophene-2,5-diyl, thieno [3 4-b] thiophene-4,6-diyl, dithieno [3,2-b: 2'3'-d] thiophene-5,5'-diyl, cyclopenta [2,1-b: 3,4-b ' Dithiophene-2,6-diyl, dithieno [3,2-b: 2 ', 3'-d] pyrrole-2,6-diyl, benzo [1,2-b: 4,5-b'] dithiophene- Examples include groups such as 2,6-diyl. The heteroarylene group may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms.

  In the chemical formula (3), the divalent heteroarylene group represented by A is preferably a group consisting of a monocyclic, condensed polycyclic or ring-aggregated thiophene derivative. Specifically, thiophene-2,5-diyl, 2,2′-bithiophene-5,5′-diyl, which may have a substituent represented by the following chemical formulas (5) to (9), thieno [3,2-b] thiophene-2,5-diyl, dithieno [3,2-b: 2 ′, 3′-d] pyrrole-2,6-diyl, benzo [1,2-b: 4,5 -B '] It is preferably any group selected from dithiophene-2,6-diyl.

〔式（５）〜（９）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１，Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７はそれぞれ同一または異なって水素原子、置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状、若しくは環状のアルキル基又はアルコキシ基であり、Ｒ^１８は、水素原子、置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状、若しくは環状のアルキル基、アルコキシ基、アリール基又はヘテロアリール基である。〕

[In the formulas (5) to (9), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ is the same or different and is a hydrogen atom, a linear, branched, or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms that may have a substituent, and R ¹⁸ is a hydrogen atom. And a C1-C20 linear, branched, or cyclic alkyl group, alkoxy group, aryl group, or heteroaryl group that may have a substituent. ]

In the chemical formulas (5) to (9), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , As the linear, branched, or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms which may have a substituent represented by R ¹⁷ and R ¹⁸ , the same as those exemplified for R ² may be used. The same thing is mentioned similarly as this substituent.

Examples of the aryl group represented by R ¹⁸ in the chemical formula (8) include aryl groups derived from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and the like. The aryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms.

Examples of the heteroaryl group represented by R ¹⁸ in the chemical formula (8) include a heteroaryl derived from a thiophene ring, a pyrrole ring, a furan ring, a selenophene ring, a silole ring, a gelmol ring, a quinoline ring, a quinoxaline ring, a quinazoline ring, and the like. An aryl group is mentioned. The heteroaryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms.

  The method for producing an alkoxythiophene derivative provided by the present invention can be produced by reacting an alkoxythiophene compound (1) with a heteroarylene compound (3) (hereinafter referred to as step 1).

（式中、Ｒ^１、Ｒ^２、Ａ、Ｍ、Ｘ^１及びＸ^２は前記定義の通り。）

(Wherein R ¹ , R ² , A, M, X ¹ and X ² are as defined above.)

There is no restriction | limiting in particular in the manufacturing method of the alkoxy thiophene compound (1) used at the process 1, For example, after lithiating 2-position of 3-alkoxy thiophene, it can manufacture by making tributyltin chloride react (nonpatent literature 4). Commercial products can also be used.
[Non-Patent Document 4] Macromolecules, 34, 4314-4323 (2001)

There is no restriction | limiting in particular in the manufacturing method of the heteroarylene compound (3) used at the process 1, For example, it can manufacture by brominating 2nd-position of 5-thieno [3,2-b] thiophene (nonpatent). Reference 5). Moreover, it can manufacture by brominating 2-position and 6-position of N-alkyl dithieno [3,2-b: 2 ', 3'-d] pyrrole (nonpatent literature 6). Commercial products can also be used.
[Non-Patent Document 5] Macromolecules, 33, 9277-9288 (2000)
[Non-Patent Document 6] Macromolecular Rapid Communications, 29, 1603-1608 (2008)

  Step 1 is performed by cross-coupling the alkoxythiophene compound (1) and the heteroarylene compound (3) in the presence of a transition metal compound in a nitrogen or argon atmosphere. Examples of the cross-coupling reaction include Tamao-Kumada-Coriu reaction using a group in which M in chemical formula (1) is represented by magnesium halide, Negishi reaction using a group represented by zinc halide, boric acid or , Suzuki-Miyaura reaction using a group represented by a borate ester, Rightda-Kosugi-Still reaction using a group represented by a trialkyltin, and the like.

As the transition metal compound used in Step 1, a transition metal compound generally used when a cross-coupling reaction is performed in organic chemical synthesis can be used. For example, a metal complex in which a phosphorus-based ligand is coordinated to nickel, palladium, or the like can be used. Examples of the palladium compound include Pd (PPh ₃ ) ₄ , Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd (OAc) _{2 and the} like, and examples of the nickel compound include NiCl ₂ (dppp) and Ni (acac) _2. Is mentioned. In addition, a phosphorus-based ligand can be allowed to coexist, and examples thereof include trialkyl phosphines, triaryl phosphines, trialkyl phosphonium salts, triaryl phosphonium salts, and the like.

  The amount of the transition metal compound used is 1 equivalent or less, preferably 0.1 equivalent or less, based on the alkoxythiophene compound (1) or heteroarylene compound (3) used.

  The reaction in step 1 is preferably performed in the presence of a solvent. The solvent may be any solvent as long as it does not affect the reaction, but is an aromatic hydrocarbon solvent such as benzene, toluene, xylene, ethylbenzene, cumene, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1, 4 -Ethers such as dioxane, halogenated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene, polar solvents such as N-methylpyrrolidone, dimethylformamide and dimethyl sulfoxide. A solvent may be used individually by 1 type and may be used in combination of 2 or more type. Further, water and an organic solvent may be mixed. When M in chemical formula (1) is boric acid or a borate ester, the reaction is performed in a suspended state using a mixed solvent of water and an organic solvent. It is preferable. When using a mixed solvent of water and an organic solvent, a quaternary ammonium salt, a phosnium salt, a crown ether or the like may be added as a phase transfer catalyst. It is preferable that the usage-amount of a solvent is 0.1 mass times-200 mass times with respect to heteroarylene compound (3) from a viewpoint of economical efficiency and the ease of post-processing.

  When M in chemical formula (1) is boric acid or borate ester in step 1, the reaction is preferably performed in the presence of a base. Examples of the base include alkali metals such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, carboxylates such as sodium acetate and potassium acetate, carbonates such as sodium carbonate and potassium carbonate, sodium phosphate, Examples thereof include phosphates such as potassium phosphate. In this case, the amount of the base used is preferably 2 equivalents or more with respect to the heteroarylene compound (3).

  The reaction temperature in step 1 varies depending on the solvent used, compound (1), compound (3) and the like, but is within the range of the reflux temperature of the solvent used from −20 ° C.

  The reaction time in step 1 varies depending on the solvent used, compound (1), compound (3), etc., but is preferably in the range of 0.5 to 72 hours, more preferably in the range of 1 to 24 hours.

  In the reaction of Step 1, if necessary, the target product can be isolated by performing operations used for isolating organic compounds such as solvent extraction, column chromatography, and recrystallization.

  By going through such steps, the desired alkoxythiophene derivative (4) can be efficiently synthesized without going through an unstable intermediate. The obtained alkoxythiophene derivative (4) is useful as a polymer material that exhibits semiconductor performance and high conductivity in a doped state and has atmospheric stability.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

<Synthesis Example 1>
Synthesis of 2-trimethylstannyl-3- [2- (2-methoxyethoxy) ethoxy] thiophene

  Under a nitrogen atmosphere, 7.0 g (34.6 mmol) of 3- [2- (2-methoxyethoxy) ethoxy] thiophene was dissolved in 10 g of diethyl ether in a 200-ml three-necked flask equipped with a thermometer. Next, 13.3 ml (34.6 mmol) of n-butyllithium hexane solution (2.6 M) was added dropwise so that the internal temperature of the reaction solution was 5 ° C. or less, and then the temperature of the reaction solution was kept at 0 ° C. Stir for hours. Thereafter, 6.9 g (34.6 mmol) of trimethyltin chloride dissolved in 20 g of diethyl ether was added dropwise so that the internal temperature of the reaction solution was 5 ° C. or lower, and then stirred at room temperature for 1 hour. Water and diethyl ether were added to the reaction mixture, and the organic layer and the aqueous layer were separated. Next, the organic layer was washed with water and concentrated under reduced pressure to obtain 12 g of 2-trimethylstannyl-3- [2- (2-methoxyethoxy) ethoxy] thiophene represented by the chemical formula (14). 94%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS, ppm) δ: 0.35 (9H, s), 3.39 (3H, s), 3.56 (2H, t, J = 4.5 Hz), 3 .69 (2H, t, J = 4.5 Hz), 3.78 (2H, t, J = 5.0 Hz), 4.12 (2H, t, J = 5.0 Hz), 6.95 (1H, d, J = 4.9 Hz), 7.46 (1H, d, J = 4.9 Hz)

<Synthesis Example 2>
Synthesis of 2-trimethylstannyl-3- [2- (2- (2-methoxyethoxy) ethoxy) ethoxy] thiophene

  In a nitrogen atmosphere in a 200 ml three-necked flask equipped with a thermometer, 8.5 g (34.6 mmol) of 3- [2- (2- (2-methoxyethoxy) ethoxy) ethoxy] thiophene was added to 10 g of diethyl ether. Dissolved. Next, 13.3 ml (34.6 mmol) of n-butyllithium hexane solution (2.6 M) was added dropwise so that the internal temperature of the reaction solution was 5 ° C. or less, and then the temperature of the reaction solution was kept at 0 ° C. Stir for hours. Thereafter, 6.9 g (34.6 mmol) of trimethyltin chloride dissolved in 20 g of diethyl ether was added dropwise so that the internal temperature of the reaction solution was 5 ° C. or lower, and then stirred at room temperature for 1 hour. Water and diethyl ether were added to the reaction mixture, and the organic layer and the aqueous layer were separated. Next, the organic layer was washed with water and then concentrated under reduced pressure to give 2-trimethylstannyl-3- [2- (2- (2-methoxyethoxy) ethoxy) ethoxy] thiophene represented by the chemical formula (15). 13 g was obtained (yield 91%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 0.34 (9H, s), 3.38 (3H, s), 3.53 to 3.86 (10H, m), 4.11 (2H M), 6.95 (1H, d, 4.9 Hz), 7.49 (1 H, d, 4.9 Hz)

<Synthesis Example 3>
Synthesis of 2-trimethylstannyl-3-dodecyloxythiophene

  In a 200-ml three-necked flask equipped with a thermometer, 9.3 g (34.6 mmol) of 3-dodecyloxythiophene was dissolved in 10 g of diethyl ether under a nitrogen atmosphere. Next, 13.3 ml (34.6 mmol) of n-butyllithium hexane solution (2.6 M) was added dropwise so that the internal temperature of the reaction solution was 5 ° C. or less, and then the temperature of the reaction solution was kept at 0 ° C. Stir for hours. Thereafter, 6.9 g (34.6 mmol) of trimethyltin chloride dissolved in 20 g of diethyl ether was added dropwise so that the internal temperature of the reaction solution was 5 ° C. or lower, and then stirred at room temperature for 1 hour. Water and diethyl ether were added to the reaction mixture, and the organic layer and the aqueous layer were separated. Next, the organic layer was washed with water and then concentrated under reduced pressure to obtain 13 g of 2-trimethylstannyl-3-dodecyloxythiophene represented by the chemical formula (16) (yield 90%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 0.34 (9H, s), 0.88 (3H, t), 1.26 to 1.43 (18H, m), 1.71 (2H M), 3.9 (2H, t), 6.94 (1H, d, 4.9Hz), 7.46 (1H, d, 4.9Hz)

<Synthesis Example 4>
Synthesis of 2,6-dibromo-N-dodecyl-dithieno [3,2-b: 2 ', 3'-d] pyrrole

  To a 300 ml three-necked flask equipped with a thermometer was added 4 g (11.5 mmol) of N-dodecyl-dithieno [3,2-b: 2 ′, 3′-d] pyrrole in a nitrogen atmosphere. 100 g of chloroform was added. Thereafter, 4.1 g (23.0 mmol) of N-bromosuccinimide dissolved in 18 g of chloroform was added dropwise at a reaction solution temperature of 0 ° C to 5 ° C. The reaction mixture was stirred for 2 hours at an internal temperature of 5 ° C. After completion of the reaction, water and hexane were added to the reaction solution, and then the organic layer and the aqueous layer were separated. By purifying the organic layer by recrystallization, the 2,6-dibromo-N-dodecyl-dithieno [3,2-b: 2 ′, 3′-d] pyrrole represented by the chemical formula (17) is converted to 4. 8 g (yield 82%) was obtained.

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 0.88 (3H, t, 6.6 Hz), 1.28 (18 H, m), 1.82 (2H, m), 4.07 (2H , T, 7.2 Hz), 7.02 (2H, s)

<Example 1>
Synthesis of 2,5-bis [3- {2- (2-methoxyethoxy) ethoxy} thiophen-2-yl] thieno [3,2-b] thiophene

  5. Trimethylstannyl-3- [2- (2-methoxyethoxy) ethoxy] thiophene obtained by the method of Synthesis Example 1 was added to a 300 ml three-necked flask equipped with a thermometer and a Dimroth condenser under a nitrogen atmosphere. 0 g (16.3 mmol) and 2,5-dibromo-thieno [3,2-b] thiophene 2.4 g (8.15 mmol) were charged. Next, 69 g of toluene, 76 g of dimethylformamide, 0.47 g (8.15 mmol) of potassium fluoride, 0.20 mg (0.640 mmol) of tri-o-tolylphosphine, 0.47 mg (0.408 mmol) of tetrakistriphenylphosphine palladium. I put it in. Thereafter, the reaction mixture was heated and stirred at an internal temperature of 90 ° C. for 3 hours. After completion of the reaction, toluene and saturated saline were added, and the organic layer and the aqueous layer were separated. This organic layer is washed with water, then added with hexane, and recrystallized to give 2,5-bis [3- (2- (2-methoxyethoxy) ethoxy) thiophene] 2 represented by the chemical formula (18). 3.6 g of yl-thieno [3,2-b] thiophene was obtained (yield 81%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 3.40 (6H, s), 3.58 (4H, m), 3.75 (4H, m), 3.92 (4H, t, 5 .0Hz), 4.30 (4H, t, 5.0Hz), 6.87 (2H, d, 5.5Hz), 7.07 (2H, d, 5.5Hz), 7.39 (2H, s) )

<Example 2>
Synthesis of 2,5-bis [3- {2- (2- (2-methoxyethoxy) ethoxy) ethoxy} thiophen-2-yl] thieno [3,2-b] thiophene

  2-Trimethylstannyl-3- [2- (2- (2-methoxyethoxy) ethoxy) ethoxy obtained by the method of Synthesis Example 2 in a 300 ml three-necked flask equipped with a thermometer and a Dimroth condenser under a nitrogen atmosphere 6.7 g (16.3 mmol) of thiophene and 2.4 g (8.15 mmol) of 2,5-dibromo-thieno [3,2-b] thiophene were charged. Next, 69 g of toluene, 76 g of dimethylformamide, 0.47 g (8.15 mmol) of potassium fluoride, 0.20 mg (0.640 mmol) of tri-o-tolylphosphine, 0.47 mg (0.408 mmol) of tetrakistriphenylphosphine palladium. I put it in. Thereafter, the reaction mixture was heated and stirred at an internal temperature of 90 ° C. for 3 hours. After completion of the reaction, toluene and saturated saline were added, and the organic layer and the aqueous layer were separated. This organic layer is washed with water, then added with hexane, and recrystallized to obtain 2,5-bis [3- {2- (2- (2-methoxyethoxy) ethoxy) represented by the chemical formula (19). Ethoxy} thiophen-2-yl] thieno [3,2-b] thiophene 4.0 g was obtained (yield 79%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 3.36 (6H, s), 3.51 to 3.78 (16H, m), 3.91 (4H, t, 5.0 Hz), 4 .29 (4H, t, 5.0 Hz), 6.88 (2H, d, 5.7 Hz), 7.07 (2H, d, 5.7 Hz), 7.26 (2H, s)

<Example 3>
Synthesis of 2,5-bis-3-dodecyloxythiophen-2-yl-thieno [3,2-b] thiophene

  In a 300 ml three-necked flask equipped with a thermometer and a Dimroth condenser, 7.0 g (16.3 mmol) of 2-trimethylstannyl-3-dodecyloxythiophene obtained by the method of Synthesis Example 3 and 2, 2.4 g (8.15 mmol) of 5-dibromo-thieno [3,2-b] thiophene was charged. Next, 69 g of toluene, 76 g of dimethylformamide, 0.47 g (8.15 mmol) of potassium fluoride, 0.20 mg (0.640 mmol) of tri-o-tolylphosphine, 0.47 mg (0.408 mmol) of tetrakistriphenylphosphine palladium. I put it in. Thereafter, the reaction mixture was heated and stirred at an internal temperature of 90 ° C. for 3 hours. After completion of the reaction, toluene and saturated saline were added, and the organic layer and the aqueous layer were separated. This organic layer was washed with water, then added with hexane and recrystallized, whereby 2,5-bis-3-dodecyloxythiophen-2-yl-thieno [3,2- b] 4.5 g of thiophene was obtained (yield 82%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 0.87 (6H, t, 6.6 Hz), 1.26 (36H, m), 1.86 (4H, m), 4.12 (4H , T, 6.5 Hz), 6.85 (2H, d, 5.4 Hz), 7.06 (2H, d, 5.4 Hz), 7.35 (2H, s)

<Example 4>
Synthesis of N-dodecyl-2,6-bis [3- (2- (2-methoxyethoxy) ethoxy) thiophene] -2-yl-dithieno [3,2-b: 2 ', 3'-d] pyrrole

  2,6-dibromo-N-dodecyl-dithieno [3,2-b: 2 ′, 3] obtained by the method of Synthesis Example 4 in a 300 ml three-necked flask equipped with a thermometer and a Dimroth condenser under a nitrogen atmosphere. '-D] 4.1 g (8.1 mmol) of pyrrole, 6.6 g (16.3 mmol) of 2-trimethylstannyl-3- [2- (2-methoxyethoxy) ethoxy] thiophene obtained by the method of Synthesis Example 1 ). Next, 69 g of toluene, 76 g of dimethylformamide, 0.47 g (8.15 mmol) of potassium fluoride, 0.20 mg (0.640 mmol) of tri-o-tolylphosphine, 0.47 mg (0.408 mmol) of tetrakistriphenylphosphine palladium. I put it in. Thereafter, the reaction mixture was heated and stirred at an internal temperature of 90 ° C. for 3 hours. After completion of the reaction, toluene and saturated saline were added, and the organic layer and the aqueous layer were separated. This organic layer was washed with water, then added with hexane and recrystallized to give N-dodecyl-2,6-bis [3- (2- (2-methoxyethoxy) ethoxy represented by the chemical formula (21). ) 5.1 g of thiophen] -2-yl-dithieno [3,2-b: 2 ′, 3′-d] pyrrole was obtained (84% yield).

¹ H-NMR (270 MHz, CDCl ₃ , TMS) δ: 0.87 (3H, t, 6.8 Hz), 1.27 (18H, m), 1.87 (2H, m), 3.39 (6H , S), 3.58 (4H, m), 3.76 (4H, m), 3.93 (4H, t, 5.0 Hz), 4.30 (4H, t, 5.0 Hz), 6. 87 (2H, d, 5.1 Hz), 7.01 (2H, d, 5.1 Hz), 7.13 (2H, s)

<Comparative Example 1>
Synthesis of 2,5-bis [3- (2- (2-methoxyethoxy) ethoxy) thiophene] 2-yl-thieno [3,2-b] thiophene

  Into a 100 ml three-necked flask equipped with a thermometer and a Dimroth condenser, 50 ml of chlorobenzene, 466 mg (1.00 mmol) of 2,5-bis (trimethyltin) -thieno [3,2-b] thiophene, 2-bromo-3 -(2- (2-methoxyethoxy) ethoxy) thiophene 562 mg (2.00 mmol), lithium chloride 42.4 mg (1.00 mmol), tris (dibenzylideneacetone) dipalladium 18.3 mg (0.0200 mmol), tri ( 24.4 mg (0.0800 mmol) of o-tolyl) phosphine was added. The reaction vessel was heated to 130 ° C. and then stirred for 8 hours. After completion of the reaction, 200 ml of toluene and 200 ml of saturated saline were added, and the organic layer and the aqueous layer were separated. The organic layer was washed twice with 200 ml of water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. Since this crude product had many by-products, it was purified by silica gel column chromatography to obtain 2,5-bis [3- (2- (2-methoxyethoxy) ethoxy) thiophene] represented by the chemical formula (18). 228 mg (0.420 mmol, 42.0%) of 2-yl-thieno [3,2-b] thiophene was obtained.

<Comparative example 2>
Synthesis of 2,5-bis-3-dodecyloxythiophen-2-yl-thieno [3,2-b] thiophene

  Into a 100 ml three-necked flask equipped with a thermometer and a Dimroth condenser, 50 ml of chlorobenzene, 466 mg (1.00 mmol) of 2,5-bis (trimethyltin) -thieno [3,2-b] thiophene, 2-bromo-3 -695 mg (2.00 mmol) of dodecyloxythiophene, 42.4 mg (1.00 mmol) of lithium chloride, 18.3 mg (0.0200 mmol) of tris (dibenzylideneacetone) dipalladium, 24.4 mg of tri (o-tolyl) phosphine ( 0.0800 mmol) was added. The reaction vessel was heated to 130 ° C. and then stirred for 8 hours. After completion of the reaction, 200 ml of toluene and 200 ml of saturated saline were added, and the organic layer and the aqueous layer were separated. The organic layer was concentrated under reduced pressure to obtain a crude product. Since this crude product had many by-products, it was purified by silica gel column chromatography to obtain 2,5-bis-3-dodecyloxythiophen-2-yl-thieno [3,2] represented by the chemical formula (20). -B] 302 mg (0.449 mmol, 44.9%) of thiophene was obtained.

  From the above results, Examples 1 to 4 using the production method of the present invention have fewer by-products than Comparative Examples 1 and 2, so that the target product can be obtained only by recrystallization. It is clear that an alkoxythiophene derivative can be obtained in a high yield, and is therefore excellent as a method for producing an alkoxythiophene derivative.

Claims (3)

The following chemical formula (1)

[In the chemical formula (1), R ¹ represents the following chemical formula (2)
R ^3- [W— (CH ₂ ) _a ] _b − (2)
(In Formula (2), R ³ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and W is an oxygen atom or a sulfur atom. And [W— (CH ₂ ) _a ] may be the same or different for W and a for each repeating unit, where a is 1 to 20 and b is a positive number from 0 to 20. Side chain,
R ² is a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms,
M is magnesium halide, zinc halide, trialkylated tin, boric acid or borate ester)
And an alkoxythiophene compound represented by the following chemical formula (3)
X ¹ -A-X ² (3)
[In Formula (3), A is a divalent heteroarylene group which may have a substituent, and X ¹ and X ² are the same or different halogen atoms, respectively]
A heteroarylene compound represented by the following formula (4) is reacted:

[In the chemical formula (4), R ¹ and R ² are the same as above]
The manufacturing method of the alkoxythiophene derivative shown by these. The method for producing an alkoxythiophene derivative according to claim 1, wherein the divalent heteroarylene group which may have a substituent is a group comprising a thiophene derivative. The method for producing an alkoxythiophene derivative according to claim 2, wherein the divalent heteroarylene group which may have a substituent is any one selected from the following chemical formulas (5) to (9);

[In the chemical formulas (5) to (9), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ is the same or different and is a hydrogen atom, a linear, branched, or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms that may have a substituent, and R ¹⁸ is a hydrogen atom. And a C1-C20 linear, branched, or cyclic alkyl group, alkoxy group, aryl group, or heteroaryl group that may have a substituent.