JPH0678334B2 - Method for producing thiophene compound - Google Patents
Method for producing thiophene compoundInfo
- Publication number
- JPH0678334B2 JPH0678334B2 JP2133586A JP13358690A JPH0678334B2 JP H0678334 B2 JPH0678334 B2 JP H0678334B2 JP 2133586 A JP2133586 A JP 2133586A JP 13358690 A JP13358690 A JP 13358690A JP H0678334 B2 JPH0678334 B2 JP H0678334B2
- Authority
- JP
- Japan
- Prior art keywords
- ether
- producing
- compound
- thiophene compound
- alkoxymethylthiophene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229930192474 thiophene Natural products 0.000 title claims description 7
- -1 thiophene compound Chemical class 0.000 title description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- KBWHYRUAHXHHFO-UHFFFAOYSA-N 3-(bromomethyl)thiophene Chemical compound BrCC=1C=CSC=1 KBWHYRUAHXHHFO-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- PYZDZZWSZBQELO-UHFFFAOYSA-N 3-(ethoxymethyl)thiophene Chemical compound CCOCC=1C=CSC=1 PYZDZZWSZBQELO-UHFFFAOYSA-N 0.000 description 2
- RCTIHQZIVLNKDZ-UHFFFAOYSA-N 3-(methoxymethyl)thiophene Chemical compound COCC=1C=CSC=1 RCTIHQZIVLNKDZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- ZDQZVKVIYAPRON-UHFFFAOYSA-N 3-phenylthiophene Chemical compound S1C=CC(C=2C=CC=CC=2)=C1 ZDQZVKVIYAPRON-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- MQAYAHVKRCESAA-UHFFFAOYSA-N S1C=C(C=C1)[K] Chemical compound S1C=C(C=C1)[K] MQAYAHVKRCESAA-UHFFFAOYSA-N 0.000 description 1
- OEJCCWIXUKNQRW-UHFFFAOYSA-N [Li]C=1C=CSC=1 Chemical compound [Li]C=1C=CSC=1 OEJCCWIXUKNQRW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002848 poly(3-alkoxythiophenes) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は，新規なチオフェン系化合物の製造方法，詳し
くは，それを重合体とすることにより有機電子材料とし
て広く利用しうるチオフェン系化合物の新規な製造方法
に関するものである。TECHNICAL FIELD The present invention relates to a novel method for producing a thiophene compound, and more specifically, to a thiophene compound that can be widely used as an organic electronic material by using it as a polymer. The present invention relates to a new manufacturing method.
（従来の技術） チオフェン等の複素環化合物を電解重合または化学酸化
重合して得られるる有機導電性組成物としては，ポリチ
オフェン，ポリ（３−アルキルチオフェン）ポリ（３−
アルコキシチオフェン），ポリベンゾチオフェン，ポリ
（３−フェニルチオフェン），ポリピロール等が知られ
ている。これら組成物は，成形性、可とう性及び溶解性
に優れており，高分子導電体として広く利用しうるもの
である。また，電解重合膜を形成，または塗膜を形成す
るなどの方法で導電基板上に薄膜を作製することにより
修飾電極として利用することができる。しかし，これら
ポリチオフェン誘導体では化学構造が極めて限定されて
いるために，電気化学的特性，溶解性，分光特性が限定
されているので，ポリチオフェン誘導体の利用分野が制
限されるのを免れなかった。(Prior Art) As an organic conductive composition obtained by electrolytic polymerization or chemical oxidative polymerization of a heterocyclic compound such as thiophene, polythiophene, poly (3-alkylthiophene) poly (3-
Alkoxythiophene), polybenzothiophene, poly (3-phenylthiophene), polypyrrole and the like are known. These compositions have excellent moldability, flexibility and solubility, and can be widely used as polymer conductors. Further, it can be used as a modified electrode by forming a thin film on a conductive substrate by a method such as forming an electrolytically polymerized film or forming a coating film. However, since these polythiophene derivatives have extremely limited chemical structures, their electrochemical properties, solubility, and spectroscopic properties are limited, and therefore the field of application of the polythiophene derivatives is unavoidable.
従来の３−アルコキシメチルチオフェンの製造方法は文
献に記載されている。（合成金属誌,26巻153−168頁,19
88年）。この方法では,3−ブロモメチルチオフェンとナ
トリウムアルコキシドとの反応により３−アルコキシメ
チルチオフェンを得ている。しかし,3−ブロモメチルチ
オフェンは市販品がないので別途合成する必要があり，
多大な労力を必要とする。また,3−ブロモメチルチオフ
ェンは極めて不安定な化合物なのでその取扱いは困難で
ある。Conventional methods for producing 3-alkoxymethylthiophenes are described in the literature. (Synthetic Metals, 26, 153-168, 19
88 years). In this method, 3-alkoxymethylthiophene is obtained by the reaction of 3-bromomethylthiophene with sodium alkoxide. However, since 3-bromomethylthiophene is not commercially available, it must be synthesized separately.
It requires a lot of work. In addition, 3-bromomethylthiophene is an extremely unstable compound, so its handling is difficult.
（発明が解決しようとする課題） 本発明は，入手容易でかつ安定な化合物を出発原料にし
て，重合することにより有機電子材料となる３−アルコ
キシメチルチオフェンを製造するための方法を提供する
ものである。(Problems to be Solved by the Invention) The present invention provides a method for producing 3-alkoxymethylthiophene as an organic electronic material by polymerizing an easily available and stable compound as a starting material. Is.
（課題を解決するための手段） 多様な特性を有するポリチオフェン系導電性組成物を開
発するために鋭意検討を行ったところ,3−アルコキシメ
チルチオフェンがこの目的に適合することを見出し，こ
の知見に基づいて３−アルコキシメチルチオフェンの新
規な製造方法を鋭意検討した結果，本発明を完成するに
至った。本発明の目的は，従来知られていなかった３−
アルコキシメチルチオフェンの新規な製造方法を提供す
ることにある。(Means for Solving the Problems) As a result of intensive studies to develop a polythiophene-based conductive composition having various properties, it was found that 3-alkoxymethylthiophene was suitable for this purpose, and The present invention has been completed as a result of earnestly investigating a novel method for producing 3-alkoxymethylthiophene based on the above. The object of the present invention has heretofore been unknown 3-
It is to provide a novel method for producing alkoxymethylthiophene.
本発明は， 一般式 （式中のＲはアルキル基） で示されるチオフェン系化合物の製造方法に関するもの
であり， 一般式 CH2X−Ｏ−Ｒ （式中のＸはハロゲンであり,Rはアルキル基） で示されるアルキルハロゲノメチルエーテルと 一般式 （式中のＭはアルカリ金属である） で示される化合物との反応によって得られる。The present invention has the general formula (Wherein R is an alkyl group) relating to a method for producing a thiophene-based compound, represented by the general formula CH 2 X—O—R (wherein X is a halogen and R is an alkyl group) Alkylhalogenomethyl ether and general formula (M in the formula is an alkali metal).
本発明の製造方法を実施するために使用する３−アルカ
リ金属化チオフェンとしては３−チエニルリチウム,3−
チエニルナトリウム,3−チエニルカリウムなどをあげる
ことができる。The 3-alkali metallized thiophene used to carry out the production method of the present invention includes 3-thienyl lithium, 3-
Examples thereof include thienyl sodium and 3-thienyl potassium.
本発明の製造方法を実施するために使用するアルキルハ
ロゲノメチルチオフェンとしては，ハロゲノメチルメチ
ルエーテル，エチルハロゲノメチルエーテル，ハロゲノ
メチルプロピルエーテル，ブチルハロゲノメチルエーテ
ル，ハロゲノメチルペンチルエーテル，ハロゲノメチル
ヘキシルエーテルなどをあげることができる。Examples of the alkylhalogenomethylthiophene used for carrying out the production method of the present invention include halogenomethylmethyl ether, ethylhalogenomethyl ether, halogenomethylpropyl ether, butylhalogenomethyl ether, halogenomethylpentyl ether, halogenomethylhexyl ether and the like. I can give you.
実施例1. 不活性ガス下で8.6gのリチウムを入れた200mlの無水エ
ーテルに100mlの無水エーテルで希釈した68.5gのｎ−ブ
チルブロマイドを−10℃で適下してｎ−ブチルリチウム
を合成した。この上澄み液を分取して−70℃に冷却し，
そこへ150mlの無水エーテルで希釈した65gの３−ブロモ
チオフェンを少量ずつ適下する。適下終了後−75〜−70
℃において30分間かくはんすると３−チエニルリチウム
が得られる。３−チエニルリチウムを−70℃に冷却し，
こゝに100mlの脱水エーテルで希釈した21.3gのクロロメ
チルメチルエーテルを−60℃以下に保持しながらゆっく
りと適下した。適下終了後15分間かくはんした後，ゆっ
くりと液温を−35℃まで上げて反応を開始させた液温を
０〜10℃まで上げて１時間かくはんした。反応終了後，
−10〜−20℃で50mlの水を加えて過剰のリチウム体を分
解した。エーテル層を分取し，無水硫酸マグネシウムで
脱水し，エーテルを留去した後，残留物を精密減圧蒸留
して３−メトキシメチルチオフェンを得た。収量20g
（収率58％）。Example 1 Synthesis of n-butyllithium by applying 68.5 g of n-butyl bromide diluted with 100 ml of anhydrous ether to 200 ml of anhydrous ether containing 8.6 g of lithium under an inert gas at -10 ° C. did. Collect the supernatant and cool to -70 ° C.
65 g of 3-bromothiophene diluted with 150 ml of anhydrous ether is added thereto little by little. After the end of the adjustment period −75 to −70
Stir for 30 minutes at ° C to give 3-thienyllithium. Cool the 3-thienyllithium to -70 ° C,
21.3 g of chloromethyl methyl ether diluted with 100 ml of dehydrated ether was slowly applied while keeping the temperature below -60 ° C. After stirring for 15 minutes, the liquid temperature was slowly raised to -35 ° C to start the reaction, and the temperature of the liquid was raised to 0 to 10 ° C, followed by stirring for 1 hour. After the reaction,
Excess lithium was decomposed by adding 50 ml of water at -10 to -20 ° C. The ether layer was separated, dried over anhydrous magnesium sulfate, the ether was distilled off, and the residue was precision distilled under reduced pressure to obtain 3-methoxymethylthiophene. Yield 20g
(Yield 58%).
沸点90.5〜91℃/53mmHg。1 H NMR δ（CDCl3）:3.33（3H,S）;4.42（2H,S）7.03
（1H,m）;7.16（1H,m）;7.25:（1H,m）。13 C NMR δ（CDCl3）:57.86,69.72,122.74,125.88,127.
23,139.31. 実施例２ 実施例１と同様して調整した３−チエニルリチウムを−
60℃以下に保持しながら,100mlの脱水エーテルで希釈し
た25gのクロロメチルエチルエーテルを適下した。適下
終了後30分間かくはんした後，液温を−30℃まで上げて
反応を開始させ，液温を０〜10℃まで上げて１時間かく
はんした。反応終了後，−10〜−20℃で50mlの水を加え
て過剰のリチウム体を分解した。エーテル層を分取し，
無水硫酸マグネシウムを脱水し，エーテル層を留去した
後，残留物を減圧蒸留して３−エトキシメチルチオフェ
ンを得た。収量19g（収率50％）。Boiling point 90.5-91 ℃ / 53mmHg. 1 H NMR δ (CDCl 3 ): 3.33 (3H, S); 4.42 (2H, S) 7.03
(1H, m); 7.16 (1H, m); 7.25: (1H, m). 13 C NMR δ (CDCl 3 ): 57.86,69.72,122.74,125.88,127.
23,139.31. Example 2 3-thienyllithium prepared in the same manner as in Example 1
While maintaining the temperature below 60 ° C, 25 g of chloromethyl ethyl ether diluted with 100 ml of dehydrated ether was applied. After stirring for 30 minutes at the end of the appropriate temperature, the temperature of the liquid was raised to -30 ° C to start the reaction, and the temperature of the liquid was raised to 0 to 10 ° C, followed by stirring for 1 hour. After completion of the reaction, 50 ml of water was added at -10 to -20 ° C to decompose excess lithium. Separate the ether layer,
After anhydrous magnesium sulfate was dehydrated and the ether layer was distilled off, the residue was distilled under reduced pressure to obtain 3-ethoxymethylthiophene. Yield 19g (yield 50%).
沸点94〜95℃/38mmHg。1 H NMR δ（CDCL3）:1.22（3H,t）;3.13（2H,m）;4.49
（2H,s）;7.06（1H,m）;7.19（1H,t）;7.27（1H,m）。13 C NMR δ（CDCl3）:15.03,65,49,67.96,122.45,125.8
2,127.21,139.63. 参考例１ 実施例１で得た３−メトキシメチルチオフェンをプロピ
レンカーボネート中−20℃でテトラブチルアンモニウム
ヘキサフルオロホスフェートを支持電解質として電解重
合したところ，白金板陽極上に1.8S/cmの導電率を示す
フィルムを得た。Boiling point 94-95 ℃ / 38mmHg. 1 H NMR δ (CDCL 3 ): 1.22 (3H, t); 3.13 (2H, m); 4.49
(2H, s); 7.06 (1H, m); 7.19 (1H, t); 7.27 (1H, m). 13 C NMR δ (CDCl 3 ): 15.03,65,49,67.96,122.45,125.8
Reference Example 1 The 3-methoxymethylthiophene obtained in Example 1 was electrolytically polymerized in propylene carbonate at −20 ° C. with tetrabutylammonium hexafluorophosphate as a supporting electrolyte, and the result was 1.8 S / cm on a platinum plate anode. A film showing a conductivity of was obtained.
参考例２ 実施例２で得た３−エトキシメチルチオフェンを参考例
１と同様にして電解重合したところ,26S/cmの導電率を
示すフィルムを得た。Reference Example 2 When 3-ethoxymethylthiophene obtained in Example 2 was subjected to electrolytic polymerization in the same manner as in Reference Example 1, a film showing a conductivity of 26 S / cm was obtained.
（発明の効果） 本発明に従うと入手しやすく，かつ安定で取扱いやすい
化合物を出発原料として，容易に３−アルコキシメチル
チオフェンを製造することができる。そして，このよう
にして得られた化合物を電解重合すると陽極上に導電性
フィルムを成形することができるので修飾電極材料及び
有機導電材料として好適である。(Effects of the Invention) According to the present invention, 3-alkoxymethylthiophene can be easily produced using a compound that is easily available, stable, and easy to handle as a starting material. Then, by electropolymerizing the compound thus obtained, a conductive film can be formed on the anode, which is suitable as a modified electrode material and an organic conductive material.
Claims (1)
ハロゲノメチルエーテルを反応させることを特徴とす
る， 一般式 （式中のＲはアルキル基を示す。） で示される３−アルコキシメチルチオフェンの製造方
法。1. A general formula characterized by reacting a 3-alkali metallized thiophene with an alkylhalogenomethyl ether. (R in the formula represents an alkyl group.) A method for producing 3-alkoxymethylthiophene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2133586A JPH0678334B2 (en) | 1990-05-23 | 1990-05-23 | Method for producing thiophene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2133586A JPH0678334B2 (en) | 1990-05-23 | 1990-05-23 | Method for producing thiophene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0426686A JPH0426686A (en) | 1992-01-29 |
| JPH0678334B2 true JPH0678334B2 (en) | 1994-10-05 |
Family
ID=15108271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2133586A Expired - Lifetime JPH0678334B2 (en) | 1990-05-23 | 1990-05-23 | Method for producing thiophene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678334B2 (en) |
-
1990
- 1990-05-23 JP JP2133586A patent/JPH0678334B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0426686A (en) | 1992-01-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |