JP3752684B2 - Thiophene derivative - Google Patents

Description

｛式中、Ｘはハロゲン原子を示し、Ｒ1 は水素、シアノ、アルキル、置換されてもよいフェニルもしくはベンジル、ＣＯＲ3 （ここでＲ3 は、アルキル、置換されてもよいフェニル又はベンジルを示す。）又は−ＣＯＯＲ4 （ここでＲ4 は、水素、アルキル、置換されてもよいフェニル又はベンジルを示す。）を示し、Ｒ2 は
【化４】

なる基〔ここでＹは直結合、分岐もしくは直鎖状の炭素数１〜１２のアルキレン、フェニレン、−ＣＯ−、−ＣＯＯ−、−ＣＯＯａｌｋ−、−ＣＯＯａｌｋＯ−、−ＣＯＯａｌｋＮ（Ｒ5 ）−（ここでＲ5 はアルキルを示す。）、−ａｌｋＣＯＯａｌｋ′Ｏ−、−ａｌｋＯ−、−ａｌｋＯａｌｋ′Ｏ−、−ａｌｋＯＣＯａｌｋ′Ｏ−（ここでａｌｋ、ａｌｋ′は分岐もしくは直鎖状の炭素数１〜１２のアルキレンを示す。）を示し、Ｚは−ＨＣ＝ＣＨ−、−ＣＨ＝ＮＮＨ−、−Ｎ＝Ｎ（Ｏ）−、−Ｃ≡Ｃ−、−ＣＯＯ−、−Ｎ＝Ｎ−、−Ｓ−又は直結合を示し、ｒは水素、ニトロ、シアノ、フッ素等のハロゲン、不斉炭素を有してもよく置換されてもよいアルキルもしくはアルコキシ、−ＣＯＲ6 （ここでＲ6 は不斉炭素を有してもよく置換されてもよいアルキル、置換されてもよいフェニルを示す。）、−ＣＯＯＲ7 又はＯＣＯＲ8 （ここでＲ7 、Ｒ8 は、水素、不斉炭素を有してもよく置換されてもよいアルキル、置換されてもよいフェニルを示す。）〕を示す。}で表わされるチオフェン誘導体である。
【０００７】
本発明のチオフェン誘導体は、下記反応式或いは公知の類似の反応を適宜選択することにより製造される。
【０００８】
【化５】

【０００９】
【化６】

【００１０】
【化７】

【００１１】
反応終了後は通常の後処理を行うことにより目的物を得ることができる。構造は、ＩＲ、ＮＭＲ、ＭＳ等から決定した。
【００１２】
本発明のチオフェン誘導体を用いた重合法反応は、ＤＭＦ、ＨＭＰＡなどの不活性溶媒中、室温〜１８０℃で行う。本発明で用いる２，５−ジハロゲノチオフェン誘導体のハロゲンは、臭素、ヨウ素が好ましく、遷移金属化合物に対し高い反応性を有する化合物が好ましい。また、触媒としての遷移金属化合物としては、テトラキス（トリフェニルホスフィン）ニッケル：Ｎｉ（ＰＰｈ3 ）4 、ビス（１，５−シクロオクタジエン）ニッケル：Ｎｉ（ｃｏｄ）2 あるいはＮｉ（ｃｏｄ）2 に中性配位子として、トリフェニルホスフィン：ＰＰｈ3 や２，２’−ビピリジン：ｂｐｙ等を加えた系、また２価ニッケル化合物を還元することによって得られた系など、ニッケルの０価錯体が一般に用いられる。触媒の量は原料有機化合物に対し、０．０１〜２当量、好ましくは０．０５〜０．８当量、更に好ましくは０．０５〜０．５当量である。後処理は通常の後処理を行うことにより目的物が得られる。
【００１３】
以上のようにして得られたポリマーは、数平均分子量は通常１，０００から２０，０００であり、これは有機溶媒可溶な好適なものである。また、共重合可能なモノマー（例えば、２，５−ジハロゲンノチオフェン誘導体など）との共重合体も可能である。
【００１４】
高分子膜得られたポリマーを有機溶媒に溶解し、例えばキャスティング法、浸漬法、スプレー法、超音波霧化法、スピンコーティング法等により成膜できる。なお、必要に応じて、本発明で得られたポリマー同志の混合、他のポリマーとの混合、安定剤、可塑剤などを含めた種々の無機、有機及び金属類等の添加物の添加など当業界においてよく知られている数多くの処理方法も用いることができる。
【００１５】
【実施例】
次に実施例を挙げて本発明を詳述する。また、本発明の実施例以外の化合物は、以下の実施例と同様の反応で製造することが可能である。
【００１６】
実施例１ モノマーの製造（ｉ）２，５−ジブロモ−３−（１１−ブロモウンデカンカルボニルオキシ）メチルチオフェンの合成
【化８】

温度計、攪拌機を付した反応容器に、１１−ブロモウンデカン酸２．９ｇ（１１．０ミリモル）と塩化チオニル４．２ｍｌを加え５０℃で３時間反応を行った。反応終了後過剰の塩化チオニルを留去し塩化１１−ブロモウンデカノイルを得た。次に別の反応容器に２，５−ジブロモ−３−ヒドロキシメチルチオフェン３．０ｇ（１１ミリモル）とトリエチルアミン２．８ｇ（２７．７ミリモル）、ＴＨＦ ２０ｍｌを加え、滴下ロートより、ＴＨＦ １５ｍｌに溶解した塩化１１−ブロモウンデカノイルを滴下し、一晩撹拌した。反応終了後ＴＨＦ、トリエチルアミンを留去し得られた生成物をクロロホルムに溶解し、水洗した。乾燥剤で脱水後カラムクロマトグラフィーで分離精製して目的物を得た。
（ii）２，５−ジブロモ−３−〔４′−（４−シアノビフェニル）オキシ〕ウンデカンカルボニルオキシメチルチオフェンの合成
【化９】

温度計、攪拌機を付した反応容器に４−ヒドロキシ−４′−シアノビフェニル０．７４ｇ（３．７６ミリモル）と無水炭酸カリウム１．３ｇ（９．３ミリモル）、アセトン４０ｍｌと触媒量のヨウ化カリウムを加え還流した。そこに（ｉ）の生成物１．９５ｇ（３．７６ミリモル）を加え２４ｈ還流した。反応終了後溶媒を留去し、クロロホルムに溶解水洗した。脱水後カラムクロマトグラフィーにより分離精製した。
【００１７】
モノマー前駆体の例を第一表に示す。
【表１】

【００１８】
前記実施例を含め、モノマーの例を第２表に示す。
【表２】

【００１９】
参考例１ ポリマーの製造
【化１０】

よく乾燥した反応容器に臭化ニッケル（II）０．０８９ｇ（０．４１ｍｍｏｌ）、トリフェニルホスフィン０．７９９ｇ（３．０４ｍｍｏｌ）と亜鉛〔酢酸中で撹拌後エーテル洗浄し真空乾燥したもの〕０．７９９ｇ（１２．２２ｍｍｏｌ）を加えた。真空ポンプで脱気後、窒素置換し、この操作を３回繰り返した。そこにモレキュラーシーブで脱水後蒸留したジメチルホルムアミド（ＤＭＦ）３ｍｌを加え、窒素雰囲気下５０℃で３０分撹拌した。赤褐色になった内容物にＤＭＦ３ｍｌに溶解した１．２８５ｇ（２．０３ｍｍｏｌ）のＮｏ．５の化合物（ＤｉＢｒＥＳＣＮ−１０）を滴下し、滴下終了後窒素雰囲気下６０℃で２０時間撹拌した。反応終了後、内容物を濃縮し、エーテルに投入して沈澱物を得た。塩酸・メタノール混合液で洗浄後、中性になるまで、メタノールで洗浄した。クロロホルムに溶解後、氷浴で冷却したエーテルに投入しポリマーを得た。
収量 ０．３８４ｇ 収率 ４０．０％
【００２０】
【発明の効果】

以上述べたように、本発明のチオフェン誘導体を用いて得られるポリマーは、有機溶媒に可溶で不純物が少なく、またこのポリマーを成形したフィルムは、熱相転と電気的活性があり、液晶性と電気的活性の２つの基本特性を同一分子内に有する。
また、上記ポリマーは有機溶媒に可溶であり、従来のスピンコード法などの塗工技術が容易であり、さらに、熱、電解等により塗膜の配列制御も可能であり、異方性を有する導電材料、誘導材料、また光スイッチ記憶材料、配向膜等の電気電子素子、光学素子等に応用できる。従って、優れた性能を有する上記ポリマーの原料となる本発明のチオフェン誘導体の産業上の利用価値は高いといえる。[0001]
[Industrial application fields]
The present invention relates to a monomer used for the production of a thiophene polymer having an excellent performance having a mesogenic group (a molecule exhibiting a liquid crystal phase alone) as a side chain.
[0002]
[Prior art]
As a method for producing a thiophene polymer having a mesogenic group as a side chain, an electrolytic oxidation polymerization method and a chemical oxidation polymerization method are known. (JP-A-2-227427, UK Pat. 2225008)
[0003]
However, these polymers contain many impurities in the polymer (for example, polymerization oxidants, by-products, etc.) and, despite the introduction of mesogenic groups, are not easily observed, such as thermal phase transitions peculiar to liquid crystal molecules. there were. In addition, these polymers are insoluble in general solvents, and detailed research and materialization are difficult.
[0004]
[Problems to be solved by the invention]
This invention is providing the monomer used for manufacture of the thiophene polymer excellent in the performance which has a mesogenic group as a side chain.
[0005]
[Means for Solving the Problems]
The present invention relates to a mesogenic group characterized by reacting a 2,5-dihalogenothiophene derivative having a mesogenic group at the 3 and / or 4 position with a metal selected from the group consisting of magnesium and zinc in the presence of a transition metal compound. Is a monomer used for the production of a thiophene polymer having as a side chain.
[0006]
When the 2,5-dihalogenothiophene derivative having a mesogenic group at the 3 and / or 4 position used in the present invention has a mesogenic group only at one of the 3 or 4 positions, the other may be substituted with a substituent. Good. These are, for example, those of the formula [I]
[Chemical 3]

{Wherein X represents a halogen atom, R1 represents hydrogen, cyano, alkyl, phenyl or benzyl which may be substituted, COR3 (wherein R3 represents alkyl, phenyl or benzyl which may be substituted) or -COOR4 (wherein R4 represents hydrogen, alkyl, phenyl or benzyl which may be substituted), and R2 represents

Wherein Y is a direct bond, branched or linear alkylene having 1 to 12 carbon atoms, phenylene, -CO-, -COO-, -COOalk-, -COOalkO-, -COOalkN (R5)-(here And R5 represents alkyl.), -AlkCOOalk'O-, -alkO-, -alkOalk'O-, -alkOCOalk'O- (wherein alk and alk 'are branched or linear carbon atoms of 1 to 12) Z represents —HC═CH—, —CH═NNH—, —N═N (O) —, —C≡C—, —COO—, —N═N—, —S—. Or r represents hydrogen, halogen such as nitro, cyano, or fluorine, alkyl or alkoxy which may have an asymmetric carbon and may be substituted, -COR6 (where R6 has an asymmetric carbon) Well replaced Alkyl, which may be substituted, and phenyl which may be substituted.), -COOR7 or OCOR8 (wherein R7 and R8 each have hydrogen, an asymmetric carbon which may be substituted or alkyl which may be substituted) Good phenyl.)]. } Is a thiophene derivative represented by:
[0007]
The thiophene derivative of the present invention is produced by appropriately selecting the following reaction formula or a known similar reaction.
[0008]
[Chemical formula 5]

[0009]
[Chemical 6]

[0010]
[Chemical 7]

[0011]
After completion of the reaction, the desired product can be obtained by carrying out ordinary post-treatment. The structure was determined from IR, NMR, MS and the like.
[0012]
The polymerization reaction using the thiophene derivative of the present invention is performed at room temperature to 180 ° C. in an inert solvent such as DMF and HMPA. The halogen of the 2,5-dihalogenothiophene derivative used in the present invention is preferably bromine or iodine, and is preferably a compound having high reactivity with the transition metal compound. Transition metal compounds as catalysts include tetrakis (triphenylphosphine) nickel: Ni (PPh3) 4, bis (1,5-cyclooctadiene) nickel: Ni (cod) 2 or Ni (cod) 2. Generally, a zero-valent complex of nickel, such as a system obtained by adding triphenylphosphine: PPh3 or 2,2'-bipyridine: bpy, or a system obtained by reducing a divalent nickel compound, is used as a functional ligand. It is done. The amount of the catalyst is 0.01 to 2 equivalents, preferably 0.05 to 0.8 equivalents, more preferably 0.05 to 0.5 equivalents, relative to the raw material organic compound. In the post-treatment, the desired product can be obtained by carrying out the usual post-treatment.
[0013]
The polymer obtained as described above usually has a number average molecular weight of 1,000 to 20,000, which is a suitable organic solvent-soluble polymer. A copolymer with a copolymerizable monomer (for example, a 2,5-dihalogenothiophene derivative or the like) is also possible.
[0014]
Polymer film The obtained polymer is dissolved in an organic solvent, and can be formed by, for example, a casting method, a dipping method, a spray method, an ultrasonic atomization method, a spin coating method, or the like. If necessary, mixing of the polymers obtained in the present invention, mixing with other polymers, addition of various inorganic, organic and metal additives including stabilizers, plasticizers, etc. Numerous processing methods well known in the industry can also be used.
[0015]
【Example】
EXAMPLES Next, an Example is given and this invention is explained in full detail. Moreover, compounds other than the Example of this invention can be manufactured by reaction similar to a following example.
[0016]
Example 1 Preparation of Monomer (i) Synthesis of 2,5-dibromo-3- (11-bromoundecanecarbonyloxy) methylthiophene

In a reaction vessel equipped with a thermometer and a stirrer, 2.9 g (11.0 mmol) of 11-bromoundecanoic acid and 4.2 ml of thionyl chloride were added and reacted at 50 ° C. for 3 hours. After completion of the reaction, excess thionyl chloride was distilled off to obtain 11-bromoundecanoyl chloride. Next, 3.0 g (11 mmol) of 2,5-dibromo-3-hydroxymethylthiophene and 2.8 g (27.7 mmol) of triethylamine and 20 ml of THF were added to another reaction vessel, and dissolved in 15 ml of THF from the dropping funnel. The 11-bromoundecanoyl chloride was added dropwise and stirred overnight. After completion of the reaction, THF and triethylamine were distilled off, and the resulting product was dissolved in chloroform and washed with water. After dehydration with a desiccant, separation and purification by column chromatography gave the desired product.
(Ii) Synthesis of 2,5-dibromo-3- [4 '-(4-cyanobiphenyl) oxy] undecanecarbonyloxymethylthiophene

In a reaction vessel equipped with a thermometer and a stirrer, 0.74 g (3.76 mmol) of 4-hydroxy-4'-cyanobiphenyl, 1.3 g (9.3 mmol) of anhydrous potassium carbonate, 40 ml of acetone and a catalytic amount of iodide Potassium was added and refluxed. Thereto was added 1.95 g (3.76 mmol) of the product of (i), and the mixture was refluxed for 24 hours. After completion of the reaction, the solvent was distilled off and the residue was dissolved in chloroform and washed with water. After dehydration, separation and purification were performed by column chromatography.
[0017]
Examples of monomer precursors are shown in Table 1.
[Table 1]

[0018]
Examples of monomers including the above examples are shown in Table 2.
[Table 2]

[0019]
Reference Example 1 Production of polymer

In a well-dried reaction vessel, 0.089 g (0.41 mmol) of nickel bromide (II), 0.799 g (3.04 mmol) of triphenylphosphine and zinc (stirred in acetic acid, washed with ether and dried in vacuo) 799 g (12.22 mmol) was added. After deaeration with a vacuum pump, the atmosphere was replaced with nitrogen, and this operation was repeated three times. Thereto was added 3 ml of dimethylformamide (DMF) which had been dehydrated after molecular sieves and distilled, and stirred at 50 ° C. for 30 minutes in a nitrogen atmosphere. 1.285 g (2.03 mmol) of No. 1 dissolved in 3 ml of DMF in the reddish brown content. Compound 5 (DiBrESCN-10) was added dropwise, and after completion of the dropwise addition, the mixture was stirred at 60 ° C. for 20 hours in a nitrogen atmosphere. After completion of the reaction, the content was concentrated and poured into ether to obtain a precipitate. After washing with a hydrochloric acid / methanol mixture, it was washed with methanol until neutral. After dissolving in chloroform, it was put into ether cooled in an ice bath to obtain a polymer.
Yield 0.384 g Yield 40.0%
[0020]
【The invention's effect】

As described above, the polymer obtained by using the thiophene derivative of the present invention is soluble in an organic solvent and has few impurities, and the film formed from this polymer has thermal phase inversion and electrical activity, and has liquid crystallinity. And two basic properties of electrical activity in the same molecule.
In addition, the polymer is soluble in an organic solvent, is easy to apply coating techniques such as a conventional spin code method, and further, can control the arrangement of the coating film by heat, electrolysis, etc. and has anisotropy. It can be applied to conductive materials, inductive materials, optical switch memory materials, electrical and electronic elements such as alignment films, optical elements, and the like. Therefore, it can be said that the industrial utility value of the thiophene derivative of the present invention, which is a raw material for the polymer having excellent performance, is high.

Claims (1)

Formula [I]

{Wherein X represents a halogen atom, R1 represents hydrogen, cyano, alkyl, phenyl or benzyl which may be substituted, COR3 (wherein R3 represents alkyl, phenyl or benzyl which may be substituted) or -COOR4 (wherein R4 represents hydrogen, alkyl, phenyl or benzyl which may be substituted), and R2 represents

Wherein Y is a direct bond, branched or linear alkylene having 1 to 12 carbon atoms, phenylene, -CO-, -COO-, -COOalk-, -COOalkO-, -COOalkN (R5)-(here And R5 represents alkyl.), -AlkCOOalk'O-, -alkO-, -alkOalk'O-, -alkOCOalk'O- (wherein alk and alk 'are branched or linear carbon atoms of 1 to 12) Z represents —HC═CH—, —CH═NNH—, —N═N (O) —, —C≡C—, —COO—, —N═N—, —S—. Or r represents hydrogen, nitro, cyano, halogen, an asymmetric carbon which may be substituted or alkyl or alkoxy, -COR6 (wherein R6 may have an asymmetric carbon) May be replaced Alkyl, optionally substituted phenyl), -COOR7 or OCOR8 (wherein R7 and R8 are hydrogen, alkyl which may have an asymmetric carbon and may be substituted, and phenyl which may be substituted). A thiophene derivative represented by: