JP2010095469A - Method for producing 3,4-dialkoxy (or alkylenedioxy) thiophene - Google Patents
Method for producing 3,4-dialkoxy (or alkylenedioxy) thiophene Download PDFInfo
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Abstract
Description
本発明は、目的物より低沸点の溶媒を用いて、窒素またはアルゴンなどの不活性ガス雰囲気下もしくは不活性ガス雰囲気かつ加圧下、３，４−ジアルコキシ（またはアルキレンジオキシ）−２，５−チオフェンジカルボン酸（以下単に「３，４−ジアルコキシチオフェンジカルボン酸」という）の脱カルボキシル化反応による３，４−ジアルコキシ（またはアルキレンジオキシ）チオフェン（以下単に「３，４−ジアルコキシチオフェン」という）の製造方法に関する。 The present invention uses 3,4-dialkoxy (or alkylenedioxy) -2,5 in an inert gas atmosphere such as nitrogen or argon or under an inert gas atmosphere and pressure using a solvent having a boiling point lower than that of the target product. -3,4-dialkoxy (or alkylenedioxy) thiophene (hereinafter simply referred to as "3,4-dialkoxythiophene") by decarboxylation reaction of thiophene dicarboxylic acid (hereinafter simply referred to as "3,4-dialkoxythiophenedicarboxylic acid") ").
これまで、３，４−ジアルコキシチオフェンジカルボン酸からの脱カルボキシル化反応による３，４−ジアルコキシチオフェンの製造方法では、溶媒としてキノリン（特許文献１）やテトラメチレンスルホン（スルホラン）、ジフェニルスルホン、ポリエチレングリコール（特許文献２）などの、生成物である３，４−ジアルコキシチオフェンよりも高沸点の特殊な溶媒が使用されてきた。また、生成物である３，４−ジアルコキシチオフェンよりも低沸点の溶媒を使用し、酸素が存在する雰囲気で３，４−ジアルコキシチオフェンジカルボン酸の脱カルボキシル化反応を行う方法も知られている（特許文献３）。
しかしながら、特許文献１に記載の方法では、反応自体が低収率であることや、残存するキノリンが後続の重合工程において妨害作用を示すことおよびキノリン回収のため、反応後の処理法としてキノリンの酸抽出が必須であった。また、特許文献２に記載の方法では、蒸留時に高真空や高温などの特殊条件が必要であった。また、溶媒の回収なしで次の反応を行うことが可能であるが、タールの蓄積に問題があった。 However, in the method described in Patent Document 1, since the reaction itself is in a low yield, the remaining quinoline exhibits an interfering action in the subsequent polymerization step, and quinoline recovery is performed as a treatment method after the reaction. Acid extraction was essential. Further, the method described in Patent Document 2 requires special conditions such as high vacuum and high temperature during distillation. Moreover, although it is possible to perform the next reaction without recovering the solvent, there was a problem in tar accumulation.
一方、特許文献３に記載の方法では、反応系に酸素あるいは空気を通気するという特殊操作が必要であった。本発明者らが追試したところ、触媒として銅粉を使用した場合において、反応は進行したものの、触媒として銅塩を使用した場合には、反応の進行はほとんど認められなかった。この結果から、酸素は、銅粉を使用した場合、これを酸化するのに必要であり、銅塩を触媒とする３，４−ジアルコキシチオフェンジカルボン酸の脱炭酸（脱カルボキシル基）においては、反応を阻害することが明らかとなった。一方、生成物であるジアルコキシチオフェンの熱安定性を酸素雰囲気下で調査した結果、着色および分解が激しいことも明らかとなった。
以上のようにこれまでの公知の製造方法を、工業的に実施するにあたっては様々の問題があった。
On the other hand, the method described in Patent Document 3 requires a special operation in which oxygen or air is passed through the reaction system. As a result of a further trial by the present inventors, when copper powder was used as the catalyst, the reaction proceeded, but when the copper salt was used as the catalyst, the progress of the reaction was hardly recognized. From this result, oxygen is necessary to oxidize copper powder when used, and in decarboxylation (decarboxylation group) of 3,4-dialkoxythiophenedicarboxylic acid using copper salt as a catalyst, It was found to inhibit the reaction. On the other hand, as a result of investigating the thermal stability of the product dialkoxythiophene in an oxygen atmosphere, it became clear that coloring and decomposition were intense.
As described above, there have been various problems in industrially implementing the known production methods so far.
本発明の目的は、高品質・高収率で３，４−ジアルコキシチオフェンを簡便に製造する方法を提供することである。 An object of the present invention is to provide a method for easily producing 3,4-dialkoxythiophene with high quality and high yield.
上記目的は以下の本発明によって達成される。すなわち、本発明は、下記一般式１または２で表される３，４−ジアルコキシチオフェンジカルボン酸を、不活性ガス雰囲気下で常圧または加圧下に、下記一般式３または４で表される３，４−ジアルコキシチオフェンよりも沸点の低い溶媒中で、２価の銅塩を触媒として脱カルボキシル化反応を行うことを特徴とする下記一般式３または４で表される３，４−ジアルコキシチオフェンの製造方法を提供する。 The above object is achieved by the present invention described below. That is, the present invention represents a 3,4-dialkoxythiophene dicarboxylic acid represented by the following general formula 1 or 2 represented by the following general formula 3 or 4 under an inert gas atmosphere at normal pressure or under pressure. A 3,4-disilane represented by the following general formula 3 or 4 is characterized in that a decarboxylation reaction is performed using a divalent copper salt as a catalyst in a solvent having a boiling point lower than that of 3,4-dialkoxythiophene. A method for producing alkoxythiophene is provided.
本発明によれば、高品質・高収率で３，４−ジアルコキシチオフェンを簡便に製造する方法を提供することができる。 According to the present invention, it is possible to provide a method for easily producing 3,4-dialkoxythiophene with high quality and high yield.
次に好ましい実施の形態を挙げて本発明をさらに詳しく説明する。本発明の方法で得られる前記一般式３または４で表される化合物は、導電性ポリチオフェンを製造するための原料であり、代表的には、３，４−エチレンジオキシチオフェン（ＥＤＯＴ、ＩＵＰＡＣ名：２，３−ジヒドロチエノ［３，４−ｂ］−１，４−ジオキシン）と呼ばれる化合物である。 Next, the present invention will be described in more detail with reference to preferred embodiments. The compound represented by the general formula 3 or 4 obtained by the method of the present invention is a raw material for producing a conductive polythiophene, typically 3,4-ethylenedioxythiophene (EDOT, IUPAC name) : 2,3-dihydrothieno [3,4-b] -1,4-dioxin).
本発明で原料として使用する前記一般式１または２で表される化合物は公知の化合物であり、下記公知文献１、２に従って製造し、本発明で使用することができる。好ましい化合物は、前記一般式１においては、Ｒ1、Ｒ2およびＲ3が置換基を有してもよい炭素原子数１〜１５の直鎖状原子団（アルキルまたアルキレン）であり、特に好ましい化合物は、Ｒ1、Ｒ2およびＲ3がエチル基（エチレン基）またはメチル基（メチレン基）である化合物である。
文献１：[Synthetic Communication,26(11), 2205 (1996)、Macromolecules,30, 2585(1997)、Tetrahedron,23,2437 (1967)、Chem.Mater.,10,896(1998)]
文献２：[J.Chem.Soc. Perkin Trans.1,2001,2595、J.prakt.Chem.,338,672(1996)、Tetrahedron Lett.,45,6049(2004)]
The compound represented by the general formula 1 or 2 used as a raw material in the present invention is a known compound, and can be produced according to the following known documents 1 and 2 and used in the present invention. In the general formula 1, a preferable compound is a linear atomic group (alkyl or alkylene) having 1 to 15 carbon atoms in which R 1 , R 2 and R 3 may have a substituent, and is particularly preferable. The compound is a compound in which R 1 , R 2 and R 3 are an ethyl group (ethylene group) or a methyl group (methylene group).
Reference 1: [Synthetic Communication, 26 (11), 2205 (1996), Macromolecules, 30, 2585 (1997), Tetrahedron, 23 , 2437 (1967), Chem. Mater., 10,896 (1998)]
Reference 2: [J. Chem. Soc. Perkin Trans. 1, 2001 , 2595, J. prakt. Chem., 338 , 672 (1996), Tetrahedron Lett., 45, 6049 (2004)]
また、本発明の製造方法は、脱カルボキシル化反応を常圧で行う場合と加圧下で行う場合に分けられる。脱カルボキシル化反応を行う場合には、出発物質である３，４−ジアルコキシチオフェンジカルボン酸を、目的物である３，４−ジアルコキシチオフェンよりも低沸点の溶媒に溶解または懸濁して行う。 The production method of the present invention can be divided into a case where the decarboxylation reaction is performed at normal pressure and a case where the decarboxylation reaction is performed under pressure. When carrying out the decarboxylation reaction, the starting material 3,4-dialkoxythiophene dicarboxylic acid is dissolved or suspended in a solvent having a lower boiling point than that of the target 3,4-dialkoxythiophene.
本発明の製造方法を不活性ガス雰囲気かつ常圧下で行う場合、溶媒としては、常圧での沸点が１２０℃以上であることが好ましい。好ましい溶媒は、アミド系溶媒であり、例えば、１−メチル−２−ピロリジノン、１，３−ジメチル−２−イミダゾリジノン、２−ピロリジノン、ε−カプロラクタム、ホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルプロパンアミドなどが使用できるが、特にＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドが望ましい。 When the production method of the present invention is carried out under an inert gas atmosphere and normal pressure, the solvent preferably has a boiling point of 120 ° C. or higher at normal pressure. Preferred solvents are amide solvents, such as 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N -Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide and the like can be used, and N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferable.
また、本発明の製造方法を不活性ガス雰囲気かつ加圧下で行う場合には、加圧下での沸点が１２０℃以上となる溶媒、例えば、水、アルコール系溶媒、ケトン系溶媒、エステル系溶媒、ニトリル系溶媒などの極性溶媒が使用できる。アルコール系溶媒としては、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、イソブタノール、ｔｅｒｔ−ブタノールなどが、ケトン系溶媒としては、アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソプロピルケトン、ジエチルケトン、エチルプロピルケトン、エチルイソプロピルケトン、ジプロピルケトン、プロピルイソプロピルケトン、ジイソプロピルケトンなどが、エステル系溶媒・ニトリル系溶媒としては、酢酸メチル、酢酸エチル、アセトニトリルなどが望ましい。また、これらの溶媒を組み合わせて使用しても構わない。出発物質である３，４−ジアルコキシチオフェンジカルボン酸が水性ペーストの場合でも、乾燥或いは共沸脱水による水の除去等の特別な操作は必要なく、そのまま本反応に使用できる。 Further, when the production method of the present invention is carried out under an inert gas atmosphere and under pressure, a solvent having a boiling point of 120 ° C. or higher under pressure, such as water, alcohol solvent, ketone solvent, ester solvent, Polar solvents such as nitrile solvents can be used. Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, and tert-butanol. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, and methyl. Isopropyl ketone, diethyl ketone, ethyl propyl ketone, ethyl isopropyl ketone, dipropyl ketone, propyl isopropyl ketone, diisopropyl ketone, and the like are preferable as the ester solvent / nitrile solvent, such as methyl acetate, ethyl acetate, and acetonitrile. Further, these solvents may be used in combination. Even when 3,4-dialkoxythiophene dicarboxylic acid as a starting material is an aqueous paste, no special operation such as drying or removal of water by azeotropic dehydration is required, and it can be used in this reaction as it is.
このような低沸点溶媒を使用する場合には、反応の圧力は、使用する溶媒によっても異なるが、反応温度が１２０℃以上となるように調整すればよく、反応の進行に順って炭酸ガスの発生により圧力が上昇するので、適当な圧力に調節してもよい。 When such a low-boiling solvent is used, the reaction pressure varies depending on the solvent used, but it may be adjusted so that the reaction temperature becomes 120 ° C. or higher. Since the pressure rises due to the occurrence of this, it may be adjusted to an appropriate pressure.
反応は溶液または懸濁液で行うことができるが、出発原料である３，４−ジアルコキシチオフェンジカルボン酸の溶媒に対する溶解度が極めて小さいことから、経済性を考慮すると、混合が可能な懸濁状態を維持できる溶媒量が好ましい。 The reaction can be carried out in solution or suspension, but since the solubility of 3,4-dialkoxythiophene dicarboxylic acid, which is the starting material, in the solvent is extremely small, in consideration of economy, it can be mixed in a suspended state. The amount of solvent that can maintain the above is preferable.
本発明における３，４−ジアルコキシチオフェンジカルボン酸の脱カルボキシル反応は、２価の銅塩を触媒として行われ、触媒としては炭酸銅、硫酸銅、酸化銅、水酸化銅、酢酸銅などを用いることができる。触媒の使用量は、出発原料である３，４−ジアルコキシチオフェンジカルボン酸に対して、１００モル％未満であればよく、一般的には２０モル％以下である。生産性および経済性を考慮すると、１０モル％以下が好ましい。 In the present invention, the decarboxylation reaction of 3,4-dialkoxythiophene dicarboxylic acid is performed using a divalent copper salt as a catalyst, and copper carbonate, copper sulfate, copper oxide, copper hydroxide, copper acetate, or the like is used as the catalyst. be able to. The usage-amount of a catalyst should just be less than 100 mol% with respect to the 3, 4- dialkoxy thiophene dicarboxylic acid which is a starting material, and is generally 20 mol% or less. Considering productivity and economy, it is preferably 10 mol% or less.
本発明の３，４−ジアルコキシチオフェンジカルボン酸の脱カルボキシル化の反応温度は、１２０〜１７０℃の範囲が好ましく、特に１２５〜１５０℃が望ましい。反応温度が１２０℃未満では、脱カルボキシル化反応が遅く、一方、反応温度が１７０℃を超えると、副反応に起因すると思われるタール分が発生する畏れがある。 The reaction temperature for the decarboxylation of the 3,4-dialkoxythiophene dicarboxylic acid of the present invention is preferably in the range of 120 to 170 ° C, particularly preferably 125 to 150 ° C. If the reaction temperature is less than 120 ° C., the decarboxylation reaction is slow. On the other hand, if the reaction temperature exceeds 170 ° C., a tar component that may be caused by a side reaction may be generated.
本発明の３，４−ジアルコキシチオフェンジカルボン酸の脱カルボキシル化反応は、窒素またはアルゴンなどの不活性ガス雰囲気下で行い、反応系に空気もしくは酸素を存在させないことが特徴である。反応系に空気もしくは酸素が存在すると、後記比較例に記載のように脱カルボキシル化反応が遅く、酸化反応に基づくと思われるタール分の発生により、収率が低下する畏れがある。 The decarboxylation reaction of 3,4-dialkoxythiophene dicarboxylic acid of the present invention is carried out in an inert gas atmosphere such as nitrogen or argon, and is characterized in that air or oxygen does not exist in the reaction system. When air or oxygen is present in the reaction system, the decarboxylation reaction is slow as described in Comparative Examples below, and the yield may decrease due to the generation of a tar component that is thought to be based on the oxidation reaction.
反応終了後、通常は溶媒を留去するが、回収される溶媒を脱カルボキシル化反応へ再利用することも可能である。また、生成物である３，４−ジアルコキシチオフェンの精製法としては、反応溶媒を除くための抽出、水洗、色や不純物を除くための活性炭処理や蒸留などがあり、これらの組み合わせにより望む純度のジアルコキシチオフェンを得ることが可能である。 After completion of the reaction, the solvent is usually distilled off, but the recovered solvent can be reused for the decarboxylation reaction. In addition, purification methods of the product 3,4-dialkoxythiophene include extraction to remove the reaction solvent, washing with water, activated carbon treatment to remove color and impurities, and distillation, etc. It is possible to obtain dialkoxythiophene.
上記の抽出操作を行う場合には、より沸点が低いジエチルエーテル、ジイソプロピルエーテルなどのエーテル系溶媒や酢酸エチルなどのエステル系溶媒、ヘキサンやトルエンなどの炭化水素系溶媒が使用できる。 When performing the above extraction operation, ether solvents such as diethyl ether and diisopropyl ether having a lower boiling point, ester solvents such as ethyl acetate, and hydrocarbon solvents such as hexane and toluene can be used.
次に比較例および実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの例に限定されるものではない。
なお、原料となる３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸は下記に示す公知文献１に記載の方法を参考にして合成した。
文献１：[Synthetic Communication,26(11), 2205 (1996)、Macromolecules,30, 2585(1997)、Tetrahedron,23,2437 (1967)、Chem.Mater.,10,896(1998)]
また、３，４−ジメトキシ−２，５−チオフェンジカルボン酸は、下記に示す公知文献２に記載の方法を参考にして合成した。
文献２：[J.Chem.Soc. Perkin Trans.1,2001,2595、J.prakt.Chem.,338,672(1996)、Tetrahedron Lett.,45,6049(2004)]
Next, although a comparative example and an Example are given and this invention is demonstrated further more concretely, this invention is not limited to these examples.
In addition, 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid as a raw material was synthesized with reference to the method described in publicly known document 1 shown below.
Reference 1: [Synthetic Communication, 26 (11), 2205 (1996), Macromolecules, 30, 2585 (1997), Tetrahedron, 23 , 2437 (1967), Chem. Mater., 10,896 (1998)]
In addition, 3,4-dimethoxy-2,5-thiophenedicarboxylic acid was synthesized with reference to the method described in publicly known document 2 shown below.
Reference 2: [J. Chem. Soc. Perkin Trans. 1, 2001 , 2595, J. prakt. Chem., 338 , 672 (1996), Tetrahedron Lett., 45, 6049 (2004)]
比較例１［銅粉を用いる反応］
酸素雰囲気下および窒素気流下にて３，４−エチレンジオキシチオフェンジカルボン酸の脱カルボキシル化反応を実施した。１００ｇのＤＭＳＯ（ジメチルスルホキシド）に、４０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および４．０ｇの銅粉末を加え、内温１２５〜１３５℃で加温し、撹拌した。各反応時間でのＥＤＯＴ（３，４−エチレンジオキシチオフェン）、中間体および原料の反応率を下記表１に示す。
Comparative Example 1 [Reaction using copper powder]
Decarboxylation reaction of 3,4-ethylenedioxythiophene dicarboxylic acid was carried out under an oxygen atmosphere and a nitrogen stream. To 100 g of DMSO (dimethyl sulfoxide), 40 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 4.0 g of copper powder were added, and the mixture was heated at an internal temperature of 125 to 135 ° C. and stirred. Table 1 below shows the reaction rates of EDOT (3,4-ethylenedioxythiophene), intermediates, and raw materials at each reaction time.
上記表１を参照すると触媒として銅粉を用いた場合には、３．０時間反応後において、酸素雰囲気下ではＥＤＯＴが有意に生成するが、窒素雰囲気化ではＥＤＯＴは殆ど生成しない。この結果は、触媒として銅粉を用いる場合には、銅粉を酸化するために酸素が必要であることを示している。 Referring to Table 1 above, when copper powder is used as a catalyst, EDOT is significantly generated in an oxygen atmosphere after reaction for 3.0 hours, but EDOT is hardly generated in a nitrogen atmosphere. This result has shown that oxygen is required in order to oxidize copper powder, when using copper powder as a catalyst.
比較例２［銅塩（酸化銅）を用いる反応］
酸素雰囲気下および窒素気流下にて３，４−エチレンジオキシチオフェンジカルボン酸の脱カルボキシル化反応を実施した。５０ｍＬのＤＭＦ（ジメチルホルムアミド）に、２０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．３６ｇの酸化銅を加え、内温１２５〜１３５℃で加温し、撹拌した。各条件でのＥＤＯＴ反応率を下記表２に示す。あわせて、各反応時間でのＥＤＯＴ、中間体および原料の反応率も下記表２に示す。
Comparative Example 2 [Reaction Using Copper Salt (Copper Oxide)]
Decarboxylation reaction of 3,4-ethylenedioxythiophene dicarboxylic acid was carried out under an oxygen atmosphere and a nitrogen stream. To 50 mL of DMF (dimethylformamide), 20 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.36 g of copper oxide were added, and the mixture was heated at an internal temperature of 125 to 135 ° C. and stirred. The EDOT reaction rate under each condition is shown in Table 2 below. In addition, Table 2 also shows the reaction rates of EDOT, intermediates, and raw materials at each reaction time.
上記表２を参照すると触媒として酸化銅を用いた場合には、３．０時間反応後において、酸素雰囲気ではＥＤＯＴの生成率は低く、実用性がないが、窒素雰囲気下ではＥＤＯＴの生成率が高いことを示している。
Referring to Table 2 above, when copper oxide is used as the catalyst, after 3.0 hours of reaction, the EDOT production rate is low in an oxygen atmosphere and is not practical, but under a nitrogen atmosphere, the EDOT production rate is low. It is high.
比較例３［銅塩（塩基性炭酸銅）を用いる反応］
酸素雰囲気下および窒素気流下にて３，４−エチレンジオキシチオフェンジカルボン酸の脱カルボキシル化反応を実施した。５０ｍＬのＤＭＦに、２０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．２５ｇの塩基性炭酸銅を加え、内温１２５〜１３５℃で加温し、撹拌した。各反応時間でのＥＤＯＴ、中間体および原料の反応率を下記表３に示す。
Comparative Example 3 [Reaction Using Copper Salt (Basic Copper Carbonate)]
Decarboxylation reaction of 3,4-ethylenedioxythiophene dicarboxylic acid was carried out under an oxygen atmosphere and a nitrogen stream. To 50 mL of DMF, 20 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.25 g of basic copper carbonate were added, and the mixture was heated at an internal temperature of 125 to 135 ° C. and stirred. Table 3 below shows the reaction rates of EDOT, intermediates, and raw materials at each reaction time.
上記表３を参照すると、比較例１と同様に触媒として塩基性炭酸銅を用いた場合には、３．０時間反応後において、酸素雰囲気ではＥＤＯＴの生成率は低く、実用性がないが、窒素雰囲気下ではＥＤＯＴの生成率が高いことを示している。
Referring to Table 3 above, when basic copper carbonate was used as a catalyst as in Comparative Example 1, the EDOT production rate was low in an oxygen atmosphere after 3.0 hours of reaction, and there was no practicality. It shows that the generation rate of EDOT is high under a nitrogen atmosphere.
実施例１
２．５ｍＬのＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）に、１．０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸と下記に示す銅触媒（Ｃｕとして５モル％）を加え、窒素雰囲気下、１３５℃の油浴で１５時間加熱撹拌した。それぞれの３，４−エチレンジオキシチオフェン（ＥＤＯＴ）生成率を下記表４に示す。
Example 1
To 2.5 mL of N, N-dimethylformamide (DMF), 1.0 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and the copper catalyst shown below (5 mol% as Cu) were added, The mixture was heated and stirred in a 135 ° C. oil bath for 15 hours under a nitrogen atmosphere. The respective 4,4-ethylenedioxythiophene (EDOT) production rates are shown in Table 4 below.
実施例２
２．５ｍＬのＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）に、１．０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸と塩基性炭酸銅２５ｍｇを加え、アルゴン雰囲気下、１３５℃の油浴で１５時間加熱撹拌したところ、生成率８８．９％でＥＤＯＴを得た。
Example 2
To 2.5 mL of N, N-dimethylformamide (DMF), 1.0 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 25 mg of basic copper carbonate were added, and 135 ° C. under an argon atmosphere. When heated and stirred in an oil bath for 15 hours, EDOT was obtained with a production rate of 88.9%.
実施例３
５０ｍＬのＤＭＦに、１５ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．３８ｇの塩基性炭酸銅を加え、窒素雰囲気下、内温１２５〜１３５℃１５時間加熱撹拌した。室温に冷却し、不溶物を濾去後、溶媒を減圧下に濃縮し、残渣１８．５ｇを得た。これに１００ｍＬのジエチルエーテルと１．０ｇの活性炭を加え、室温下３０分間撹拌後、不溶物を濾去した。濾液に２０ｍＬの水を加え、抽出操作を行った。有機層の溶媒を減圧下に留去し、７．４ｇのＥＤＯＴを得た。
Example 3
To 50 mL of DMF, 15 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.38 g of basic copper carbonate were added, and the mixture was heated and stirred for 15 hours at an internal temperature of 125 to 135 ° C. in a nitrogen atmosphere. After cooling to room temperature and removing insolubles by filtration, the solvent was concentrated under reduced pressure to obtain 18.5 g of a residue. To this, 100 mL of diethyl ether and 1.0 g of activated carbon were added, and the mixture was stirred at room temperature for 30 minutes. 20 mL of water was added to the filtrate, and extraction operation was performed. The solvent of the organic layer was distilled off under reduced pressure to obtain 7.4 g of EDOT.
実施例４
５０ｍＬのＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）に１５ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．３８ｇの塩基性炭酸銅を加え、窒素雰囲気下、内温１２５〜１３５℃で撹拌しながら、１５時間加温した。室温に冷却し、不溶物を濾去後、溶媒を減圧下に濃縮し、残渣１７．８ｇを得た。これに１００ｍＬのジエチルエーテルと１．０ｇの活性炭を加え、室温下３０分間撹拌後、活性炭を濾去した。濾液に２０ｍＬの水を加え、抽出操作を行った。有機層の溶媒を減圧下に留去し、５．７ｇのＥＤＯＴを得た。
Example 4
To 50 mL of N, N-dimethylacetamide (DMAc), 15 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.38 g of basic copper carbonate are added, and the internal temperature is 125 to 135 under a nitrogen atmosphere. The mixture was warmed for 15 hours while stirring at ° C. After cooling to room temperature and removing insolubles by filtration, the solvent was concentrated under reduced pressure to obtain 17.8 g of a residue. To this, 100 mL of diethyl ether and 1.0 g of activated carbon were added, and the mixture was stirred at room temperature for 30 minutes, and then the activated carbon was removed by filtration. 20 mL of water was added to the filtrate, and extraction operation was performed. The solvent of the organic layer was distilled off under reduced pressure to obtain 5.7 g of EDOT.
実施例５
１２５ｍＬのＤＭＦに、３７．５ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．９４ｇの塩基性炭酸銅を加え、窒素雰囲気下、内温１２５〜１３５℃で撹拌しながら１５時間加温した。室温に冷却し、不溶物を濾去後、溶媒を減圧下に濃縮し、残渣５５．４ｇを得た。これに２５０ｍＬの酢酸エチルと２．５ｇの活性炭を加え、室温下３０分間撹拌後、活性炭を濾去した。濾液に５０ｍＬの水を加え、抽出操作を行った。有機層の溶媒を減圧下に留去し、２１．５ｇのＥＤＯＴを得た。
Example 5
To 125 mL of DMF, 37.5 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.94 g of basic copper carbonate are added and stirred at an internal temperature of 125 to 135 ° C. in a nitrogen atmosphere. Warmed for 15 hours. After cooling to room temperature, insolubles were removed by filtration, and the solvent was concentrated under reduced pressure to obtain 55.4 g of a residue. To this were added 250 mL of ethyl acetate and 2.5 g of activated carbon, and the mixture was stirred at room temperature for 30 minutes, and then the activated carbon was filtered off. 50 mL of water was added to the filtrate, and extraction operation was performed. The solvent of the organic layer was distilled off under reduced pressure to obtain 21.5 g of EDOT.
実施例６
３．４ＬのＤＭＦを攪拌機つきのフラスコに入れ、２．０ｋｇの湿体の３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸（乾体換算：１．５ｋｇ）および３６ｇの炭酸銅を加えた。混合物を加熱し、窒素雰囲気下、内温６０〜７５℃、内圧１６０〜４０ｔｏｒｒで共沸脱水を行い、水約５５０ｇを留出させた。留出した量のＤＭＦ３４２ｍＬを補充後、反応温度を１２５〜１３８℃とし、混合物を１３時間攪拌した。反応液を室温に冷却後、不溶物を濾去後、内温７５〜１００℃、内圧４０〜１９ｔｏｒｒで溶媒を留去した。内圧を１．６〜０．９ｔｏｒｒとし、内温４８〜１００℃で蒸留を行い、留出分７２３ｇ（ＥＤＯＴとしての純度８８％）を得た。得られた液体を７２５ｍＬで２回、３６２ｍＬで１回水洗を行い、ＥＤＯＴ粗体６１４ｇ（純度９８％）を得た。ＥＤＯＴ粗体をさらに蒸留し、５８０ｇの精製ＥＤＯＴ（純度９９％）を得た。
Example 6
Place 3.4 L of DMF in a flask with a stirrer and add 2.0 kg of wet 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid (dry body equivalent: 1.5 kg) and 36 g of copper carbonate. It was. The mixture was heated and subjected to azeotropic dehydration under a nitrogen atmosphere at an internal temperature of 60 to 75 ° C. and an internal pressure of 160 to 40 torr to distill about 550 g of water. After supplementing 342 mL of the distilled amount of DMF, the reaction temperature was 125 to 138 ° C., and the mixture was stirred for 13 hours. The reaction solution was cooled to room temperature, insolubles were filtered off, and the solvent was distilled off at an internal temperature of 75 to 100 ° C. and an internal pressure of 40 to 19 torr. Distillation was conducted at an internal temperature of 1.6 to 0.9 torr and an internal temperature of 48 to 100 ° C. to obtain 723 g of a distillate (purity 88% as EDOT). The obtained liquid was washed with water twice at 725 mL and once at 362 mL to obtain 614 g (purity 98%) of an EDOT crude product. The crude EDOT was further distilled to obtain 580 g of purified EDOT (purity 99%).
実施例７（３，４−ジメトキシチオフェンへの適用）
２．５ｍＬのＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）に、１．０ｇの３，４−ジメトキシチオフェンジカルボン酸と塩基性炭酸銅２５ｍｇを加え、窒素雰囲気下、１３５℃の油浴で１５時間加熱撹拌したところ、生成率５８．８％で３，４−ジメトキシチオフェンを得た。
Example 7 (Application to 3,4-dimethoxythiophene)
To 2.5 mL of N, N-dimethylformamide (DMF), 1.0 g of 3,4-dimethoxythiophenedicarboxylic acid and 25 mg of basic copper carbonate are added, and the mixture is heated and stirred in an oil bath at 135 ° C. for 15 hours under a nitrogen atmosphere. As a result, 3,4-dimethoxythiophene was obtained with a production rate of 58.8%.
実施例８
１００ｍＬの下記表５の溶媒に、３０．０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸と塩基性炭酸銅０．７５ｇを加え、窒素加圧６．０ｋｇ／ｃｍ2とした後に、加温し内温１３５〜１４０℃で撹拌を行った。反応の進行とともに二酸化炭素が発生し、圧力が上昇したので、内圧が７．０ｋｇ／ｃｍ2に到達した時点で圧力を放出して６．０ｋｇ／ｃｍ2に調整する操作を繰り返し行った。検討溶媒のそれぞれの反応時間におけるＥＤＯＴ生成率を下記表５に示す。
Example 8
To 100 mL of the solvent shown in Table 5 below, 30.0 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.75 g of basic copper carbonate were added to obtain a nitrogen pressure of 6.0 kg / cm 2 . Thereafter, the mixture was heated and stirred at an internal temperature of 135 to 140 ° C. Carbon dioxide is generated as the reaction proceeds, since the pressure is increased, the internal pressure was repeated operation for adjusting the 6.0 kg / cm 2 by releasing pressure when it reaches the 7.0 kg / cm 2. Table 5 below shows the EDOT production rate in each reaction time of the studied solvents.
実施例９
１００ｍＬのＩＰＡに、３０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．７５ｇの塩基性炭酸銅を加え、窒素加圧６．０ｋｇ／ｃｍ2とした後、撹拌下、内温１４０℃で加温した。内圧６．０〜７．０ｋｇ／ｃｍ2を維持しながら１９時間反応を行い、室温に冷却後、反応液に２．０ｇの活性炭を加え、室温下３０分間撹拌した。活性炭を濾去後、溶媒を減圧下に濃縮し、ＥＤＯＴ１．４９ｇを得た。
Example 9
To 100 mL of IPA, 30 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.75 g of basic copper carbonate were added, and the pressure of nitrogen was adjusted to 6.0 kg / cm 2 . The internal temperature was 140 ° C. The reaction was carried out for 19 hours while maintaining an internal pressure of 6.0 to 7.0 kg / cm 2, and after cooling to room temperature, 2.0 g of activated carbon was added to the reaction solution and stirred at room temperature for 30 minutes. After the activated carbon was filtered off, the solvent was concentrated under reduced pressure to obtain 1.49 g of EDOT.
実施例１０
１００ｍＬのアセトニトリルに、３０ｇの３，４−エチレンジオキシ−２，５−チオフェンジカルボン酸および０．７５ｇの塩基性炭酸銅を加え、窒素加圧６．０ｋｇ／ｃｍ2とした後、撹拌下、内温１４０℃で加温した。内圧６．０〜７．０ｋｇ／ｃｍ2を維持しながら１０時間反応を行い、室温に冷却した。不溶物を濾去後、溶媒を減圧下に濃縮し、ＥＤＯＴ１６．２ｇを得た。
Example 10
To 100 mL of acetonitrile, 30 g of 3,4-ethylenedioxy-2,5-thiophenedicarboxylic acid and 0.75 g of basic copper carbonate were added, and the pressure of nitrogen was adjusted to 6.0 kg / cm 2 . The internal temperature was 140 ° C. While maintaining an internal pressure of 6.0 to 7.0 kg / cm 2 , the reaction was performed for 10 hours, and the mixture was cooled to room temperature. The insoluble material was removed by filtration, and the solvent was concentrated under reduced pressure to obtain 16.2 g of EDOT.
実施例１１
１００ｍＬのアセトニトリルに、１０．０ｇの３，４−ジメトキシチオフェンジカルボン酸と塩基性炭酸銅０．２５ｇを加え、窒素加圧６．０ｋｇ／ｃｍ2とした後、撹拌下、内温１４０℃で加温した。内圧６．０〜７．０ｋｇ／ｃｍ2を維持しながら１０時間反応を行ったところ、生成率５３．７％で３，４−ジメトキシチオフェンを得た。
なお、上記においてＥＤＯＴの純度および３，４−ジメトキシチオフェンの生成率の測定は、ＨＰＬＣによる絶対検量線法で行った。
Example 11
To 100 mL of acetonitrile, 10.0 g of 3,4-dimethoxythiophenedicarboxylic acid and 0.25 g of basic copper carbonate are added to adjust the nitrogen pressure to 6.0 kg / cm 2, and then the mixture is heated at an internal temperature of 140 ° C. with stirring. Warm up. When the reaction was carried out for 10 hours while maintaining the internal pressure of 6.0 to 7.0 kg / cm 2 , 3,4-dimethoxythiophene was obtained with a production rate of 53.7%.
In the above, the purity of EDOT and the production rate of 3,4-dimethoxythiophene were measured by the absolute calibration curve method by HPLC.
本発明によれば、高品質・高収率でジアルコキシチオフェンを簡便に製造する方法を提供することができる。本発明の特長は、ジアルコキシチオフェンより低沸点の溶媒の使用することにある。なお、本発明で得られるジアルコキシチオフェンは導電性ポリマーであるポリチオフェンの原料として有用である。 According to the present invention, a method for easily producing dialkoxythiophene with high quality and high yield can be provided. The feature of the present invention resides in the use of a solvent having a lower boiling point than dialkoxythiophene. The dialkoxythiophene obtained in the present invention is useful as a raw material for polythiophene which is a conductive polymer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102633811A (en) * | 2012-05-04 | 2012-08-15 | 苏州大学 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
| CN103254169A (en) * | 2013-04-18 | 2013-08-21 | 青岛和成医药化工有限公司 | Process for synthesizing 3, 4-dimethoxythiophene |
| JP2013533216A (en) * | 2010-05-18 | 2013-08-22 | コーニング インコーポレイテッド | Process for producing condensed thiophene |
| CN106366094A (en) * | 2016-08-31 | 2017-02-01 | 贝利化学（张家港）有限公司 | Decarboxylation method of thieno[3,4-b]-1,4-dioxa-5,7-dicarboxylic acid |
| CN112209945A (en) * | 2020-11-10 | 2021-01-12 | 湖北吉和昌化工科技有限公司 | Synthesis process of 3, 4-ethylenedioxythiophene |
| CN112979927A (en) * | 2019-12-17 | 2021-06-18 | 深圳新宙邦科技股份有限公司 | Composition, polymer for capacitor and capacitor |
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2008
- 2008-10-16 JP JP2008267739A patent/JP2010095469A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013533216A (en) * | 2010-05-18 | 2013-08-22 | コーニング インコーポレイテッド | Process for producing condensed thiophene |
| CN102633811A (en) * | 2012-05-04 | 2012-08-15 | 苏州大学 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
| CN103254169A (en) * | 2013-04-18 | 2013-08-21 | 青岛和成医药化工有限公司 | Process for synthesizing 3, 4-dimethoxythiophene |
| CN106366094A (en) * | 2016-08-31 | 2017-02-01 | 贝利化学（张家港）有限公司 | Decarboxylation method of thieno[3,4-b]-1,4-dioxa-5,7-dicarboxylic acid |
| CN112979927A (en) * | 2019-12-17 | 2021-06-18 | 深圳新宙邦科技股份有限公司 | Composition, polymer for capacitor and capacitor |
| CN112209945A (en) * | 2020-11-10 | 2021-01-12 | 湖北吉和昌化工科技有限公司 | Synthesis process of 3, 4-ethylenedioxythiophene |
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