JP2007099736A - Benzothiophene compound - Google Patents
Benzothiophene compound Download PDFInfo
- Publication number
- JP2007099736A JP2007099736A JP2005294967A JP2005294967A JP2007099736A JP 2007099736 A JP2007099736 A JP 2007099736A JP 2005294967 A JP2005294967 A JP 2005294967A JP 2005294967 A JP2005294967 A JP 2005294967A JP 2007099736 A JP2007099736 A JP 2007099736A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- substituted
- compound
- benzodithiophene
- 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.)
- Granted
Links
- 0 **(*)c1c(*)c(c2c(c(*)c3*)[s]c(C(*)(*)*)c2*)c3[s]1 Chemical compound **(*)c1c(*)c(c2c(c(*)c3*)[s]c(C(*)(*)*)c2*)c3[s]1 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
本発明は、反応性官能基を有する新規な製造中間体(中間原料体)に関するものであり、特に、π共役系高分子製造のための中間体で、得られるπ共役系高分子が有機エレクトロニクス用素材として極めて有用であるベンゾジチオフェン化合物に関する。 The present invention relates to a novel production intermediate (intermediate raw material) having a reactive functional group, and in particular, an intermediate for producing a π-conjugated polymer, and the obtained π-conjugated polymer is an organic electronics. The present invention relates to a benzodithiophene compound that is extremely useful as a raw material.
有機材料の発光特性や電荷輸送特性を利用して、有機エレクトロルミネッセンス素子や、有機トランジスタ素子が提案されている。これらの素子に有機材料を用いることにより、軽量、安価、低製造コスト、フレキシブル等の利点が期待される。 Organic electroluminescence elements and organic transistor elements have been proposed by utilizing the light emission characteristics and charge transport characteristics of organic materials. By using an organic material for these elements, advantages such as light weight, low cost, low manufacturing cost, and flexibility are expected.
従来では、有機薄膜EL素子用の材料として、低分子系および高分子系の様々な材料が報告されている。低分子系においては、種々の積層構造の採用により高効率化の実現が、またドーピング法をうまくコントロールすることにより耐久性の向上が報告されている。しかし、低分子集合体の場合には、長時間における経時による膜状態の変化が生じることが報告されており、膜の安定性に関して本質的な問題点を抱えている。 Conventionally, various materials of low molecular weight and high molecular weight have been reported as materials for organic thin film EL elements. In low molecular weight systems, it has been reported that high efficiency is achieved by employing various laminated structures, and that durability is improved by well controlling the doping method. However, in the case of low molecular aggregates, it has been reported that the film state changes with time over a long period of time, and has an essential problem with respect to the stability of the film.
一方、高分子系材料においては、これまで、主にPPV(poly−p−phenylenevinylene)系列やpoly−thiophene等のπ共役系高分子について精力的に検討が行われてきた。 On the other hand, in the case of polymer materials, energetic studies have been made mainly on π-conjugated polymers such as PPV (poly-p-phenylene vinylene) series and poly-thiophene.
しかしながら、これらの材料系は純度を上げることが困難であることや、本質的に蛍光量子収率が低いことが問題点として挙げられ、高性能なEL素子は得られていないのが現状である。またπ共役高分子主鎖中にベンゾジチオフェン部位を含む高分子材料も提案されている(例えば、特許文献1参照)。 However, it is difficult to increase the purity of these material systems and the intrinsically low fluorescence quantum yield is cited as a problem, and at present, high-performance EL devices have not been obtained. . A polymer material containing a benzodithiophene moiety in the π-conjugated polymer main chain has also been proposed (see, for example, Patent Document 1).
高分子材料は本質的にガラス状態が安定であることを考慮すると、高蛍光量子効率を付与することができれば優れたEL素子の構築が可能となるため、この分野でさらなる改良が行われている。 In consideration of the fact that polymer materials are inherently stable in the glass state, if high fluorescence quantum efficiency can be imparted, an excellent EL device can be constructed, and further improvements have been made in this field. .
一方、有機薄膜トランジスタ素子においても、低分子系および高分子系の様々な材料が報告されている。例えば低分子材料ではペンタセン、フタロシアニン、フラーレン、アントラジチオフェン、チオフェンオリゴマー、ビスジチエノチオフェンなどが、また高分子材料ではポリチオフェン(例えば、非特許文献1参照)、ポリチエニレンビニレン(例えば、非特許文献2参照)などの幾つかの材料が挙げられる。
しかし、上記の材料においても、低分子系では膜の安定性に関する問題が、高分子系では純度に起因する低性能の問題があり、さらなる改良が望まれている。
However, even in the above materials, there is a problem regarding the stability of the film in the low molecular system, and there is a problem in the low performance due to the purity in the high molecular system, and further improvement is desired.
本発明は、上記従来技術の実状に鑑みてなされたものであって、有機エレクトロニクス用のπ共役系高分子を製造するための、公知の反応を利用して様々なπ共役系高分子に誘導できる反応性官能基を含有する新規な製造中間体を提供することを目的とする。 The present invention has been made in view of the above-described prior art, and is derived to various π-conjugated polymers using known reactions for producing π-conjugated polymers for organic electronics. It is an object of the present invention to provide a novel production intermediate containing a reactive functional group.
本発明者らは鋭意検討した結果、π共役系高分子を製造するための反応性官能基をもつベンゾジチオフェン構造を有する製造中間体を用いることにより、上記課題が解決されることを見出し本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a production intermediate having a benzodithiophene structure having a reactive functional group for producing a π-conjugated polymer. The invention has been completed.
上記の課題を解決するために、請求項1に記載の発明は、下記式(I)で表されることを特徴とするベンゾジチオフェン化合物を提供する。
In order to solve the above problems, the invention according to
また、請求項2に記載の発明は、下記式(II)で表されるベンゾジチオフェン化合物であることを特徴とする。
The invention described in
本発明によれば、本発明における請求項1または2の構成により、新規なアリレンビニレン型ベンゾジチオフェン重合体の製造やベンゾジチオフェンへの更なる機能性官能基による修飾が可能となる。 According to the present invention, according to the constitution of the first or second aspect of the present invention, it is possible to produce a novel arylene vinylene type benzodithiophene polymer and to modify the benzodithiophene with further functional functional groups.
以下、本発明の化合物を実施形態により、詳細に説明する。
まず本発明のベンゾジチオフェン誘導体の製造方法について説明する。
Hereinafter, the compound of the present invention will be described in detail by embodiments.
First, a method for producing the benzodithiophene derivative of the present invention will be described.
(式(I)中、Zは−PO(OR’)2(式中R’は低級アルキル基を表す)または
−P+R’’3Y−(式中R’’はフェニル基あるいはアルキル基を、Yはハロゲン原子を表す)を表し、R1〜R8は、それぞれ独立に、水素原子、置換または無置換のアルキル基またはアルコキシ基、置換或いは無置換の芳香族炭化水素基または芳香族複素環基を表す。)
および、
(In the formula (I), Z represents —PO (OR ′) 2 (wherein R ′ represents a lower alkyl group) or —P + R ″ 3 Y— (where R ″ represents a phenyl group or an alkyl group, Y represents a halogen atom), and R 1 to R 8 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group or an alkoxy group, a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic ring. Represents a group.)
and,
式(II)で表されるベンゾジチオフェン誘導体は、ベンゾジチオフェンから容易に誘導可能である。例えばJournal of Organic Chemistry,32,3093,1967.等に記載されている下記方法に従って式(1)により、ベンゾジチオフェンを合成した後、 The benzodithiophene derivative represented by the formula (II) can be easily derived from benzodithiophene. For example, after synthesizing benzodithiophene by the formula (1) according to the following method described in Journal of Organic Chemistry, 32, 3093, 1967.
例えば下記式(2)Vilsmeier反応、 For example, the following formula (2) Vilsmeier reaction,
あるいは、アリールリチウム化合物(Ar−H)と、DMF(ジメチルホルムアミド)、N−ホルミルモルホリン、N−ホルミルピペリジン等をはじめとするカルボニル化剤とを、式(3)で示す反応、 Alternatively, an aryllithium compound (Ar—H) and a carbonylating agent such as DMF (dimethylformamide), N-formylmorpholine, N-formylpiperidine and the like are represented by the reaction represented by formula (3):
あるいは、下記式(4)に示すGatterman反応、 Alternatively, a Gatterman reaction represented by the following formula (4):
等の下記式(5)に示す反応を用いて下記のようにジカルボニル化合物を合成する。 A dicarbonyl compound is synthesized as follows using a reaction represented by the following formula (5).
さらにこのジカルボニル化合物を水素化ホウ素ナトリウムや水素化リチウムアルミニウム等をはじめとする還元試薬を用いてアルコールへ誘導する(式(6)参照)。 Further, this dicarbonyl compound is derived into an alcohol using a reducing reagent such as sodium borohydride or lithium aluminum hydride (see formula (6)).
さらに該アルコールの水酸基を塩化チオニルや臭化リン等をはじめとするハロゲン化試薬によりハロゲンに置換する(式(7)参照)。 Furthermore, the hydroxyl group of the alcohol is substituted with halogen by a halogenating reagent such as thionyl chloride or phosphorus bromide (see formula (7)).
これにより、式(II)で表されるベンゾジチオフェン誘導体を得る事ができる。或いはパラホルムアルデヒドとハロゲン化水素等を用いて直接ベンゾジチオフェンをハロメチル化する方法などによっても得る事ができる(式(8)参照)。 Thereby, a benzodithiophene derivative represented by the formula (II) can be obtained. Alternatively, it can also be obtained by a method of directly halomethylating benzodithiophene using paraformaldehyde and hydrogen halide or the like (see formula (8)).
または、Journal of Organic Chemistry, 32, 3093, 1967. 等に記載されている下記方法に従ってメチル基を有するベンゾジチオフェンを合成した後(式(9)参照)、 Alternatively, after synthesizing a benzodithiophene having a methyl group according to the following method described in Journal of Organic Chemistry, 32, 3093, 1967., etc. (see formula (9)),
過酸化物と、例えばN−ブロモサクシンイミドやN−クロロサクシンイミドなどのハロゲン化試薬により、ラジカル的にメチル基をハロゲン化する事によっても合成できる(式(10)参照)。 It can also be synthesized by radically halogenating a methyl group with a peroxide and a halogenating reagent such as N-bromosuccinimide or N-chlorosuccinimide (see formula (10)).
次に、式(I)で表されるベンゾジチオフェンのリン化合物について説明する。
式(I)で表されるベンゾジチオフェンのリン化合物は、上記で得られた式(II)で表されるベンゾジチオフェンのハロメチル体から容易に誘導する事が可能である。
例えばMichaelis−Arbuzov反応として知られるトリアルキルホスホン酸エステル(P(OR)3中Rは低級アルキル基を表す)との反応(式(11)参照)
Next, the phosphorus compound of benzodithiophene represented by the formula (I) will be described.
The phosphorus compound of benzodithiophene represented by formula (I) can be easily derived from the halomethyl form of benzodithiophene represented by formula (II) obtained above.
For example, a reaction with a trialkylphosphonic acid ester (R in P (OR) 3 represents a lower alkyl group) known as Michaelis-Arbuzov reaction (see formula (11))
あるいは、前記ヒドロキシメチル化合物からもトリアルキルホスホン酸エステル(式:P(OR)3中、Rは低級アルキル基を表す。)と、ヨウ化物を用いて同様に式(I)で表されるベンゾジチオフェンのリン化合物を合成する事ができる(式(12)参照)。 Alternatively, from the hydroxymethyl compound, a trialkylphosphonic acid ester (in the formula: P (OR) 3 , R represents a lower alkyl group) and an iodide are also used to represent the benzoic acid represented by the formula (I). A phosphorus compound of dithiophene can be synthesized (see formula (12)).
式(I)で示される化合物のうち、Zが−P+R’’3Y−(式中R’’はフェニル基あるいはアルキル基を、Yはハロゲン原子を表す)で示される化合物でも、上記で得られた式(II)で表されるベンゾジチオフェンのハロメチル体から容易に誘導する事が可能である。この場合、上記で得られた式(I)をホスフィン化合物(ホスフィン化合物PR3中、Rはフェニル基またはアルキル基をあらわす。)と反応させればよく、これはいわゆるWitting試薬の調製として知られている(式(13)参照)。 Among the compounds represented by the formula (I), the compound represented by Z is —P + R ″ 3 Y— (wherein R ″ represents a phenyl group or an alkyl group, and Y represents a halogen atom). It can be easily derived from the halomethyl form of benzodithiophene represented by the formula (II). In this case, the formula (I) obtained above may be reacted with a phosphine compound (in the phosphine compound PR 3 , R represents a phenyl group or an alkyl group), which is known as preparation of a so-called Witting reagent. (See formula (13)).
またはホスホン酸エステルの場合同様に、前記ヒドロキシメチル化合物からも合成する事ができる(式(14)参照)。 Alternatively, it can be synthesized from the hydroxymethyl compound as in the case of a phosphonate (see formula (14)).
本発明における式(I)或いは(II)で表される化合物を用いる事により、有機エレクトロニクス用途に有用である新規なπ共役系重合体を容易に得る事ができる。 By using the compound represented by the formula (I) or (II) in the present invention, a novel π-conjugated polymer useful for organic electronics can be easily obtained.
例えば式(II)で表される化合物に、溶媒中、2倍モルの塩基を作用させると容易に重合反応が進行し、アリレンビニレンタイプの重合体を得る事が可能である。これはGILCH重合と呼ばれ、その詳細は例えばMacromolecules,1999,32,4295−4932.等に記載されている(式(15)参照)。 For example, when a 2-fold mole of base is allowed to act on the compound represented by the formula (II) in a solvent, the polymerization reaction easily proceeds, and an arylene vinylene type polymer can be obtained. This is called GILCH polymerization, and details thereof are described in, for example, Macromolecules, 1999, 32, 4295-4932. (See formula (15)).
或いは式(I)で表されるリン化合物を等モルのジカルボニル化合物共存下、塩基を作用させる事によっても重合体が得られる。本反応はWittig反応、あるいはWittig−Horner反応として知られ、本法によりアリレンビニレンタイプの共重合体を得る事が可能である。特に式(I)で表されるリン化合物を用いたWittig−Horner反応やWittig反応は反応操作の簡便さから非常に有効である。Wittig−Horner反応を用いた本発明における重合体の製造方法について、さらに詳細に説明する。 Alternatively, the polymer can be obtained by reacting the phosphorus compound represented by the formula (I) with a base in the presence of an equimolar amount of a dicarbonyl compound. This reaction is known as Wittig reaction or Wittig-Horner reaction, and an arylene vinylene type copolymer can be obtained by this method. In particular, the Wittig-Horner reaction and Wittig reaction using the phosphorus compound represented by the formula (I) are very effective because of the simplicity of the reaction operation. The method for producing the polymer in the present invention using the Wittig-Horner reaction will be described in more detail.
Wittig−Horner反応を用いて重合体を合成する場合、下記の式で示されるように、式(I)で示されるホスホン酸エステル化合物と、アルデヒド化合物とが、化学量論的にほぼ等モル量で存在する溶液と、その2倍モル量以上の塩基を混合させることにより重合反応が進行し、重合体を得ることができる(式(16)参照)。 When a polymer is synthesized using the Wittig-Horner reaction, the phosphonic acid ester compound represented by the formula (I) and the aldehyde compound are approximately stoichiometrically equimolar as shown by the following formula. Is mixed with a base at least twice as much as the amount of the base, whereby the polymerization reaction proceeds and a polymer can be obtained (see formula (16)).
得られる重合体はビニレン単位によって結合した共役ポリマーである。このため、得られたポリマーは発光特性、電荷輸送特性等に優れた有機エレクトロニクス材料として非常に有用な材料を得る事ができる。なお、本反応による重合体の製造の詳細は特開2004−18831号公報に記載されている。 The resulting polymer is a conjugated polymer linked by vinylene units. For this reason, the obtained polymer can obtain a very useful material as an organic electronic material excellent in light emission characteristics, charge transport characteristics and the like. Details of the production of the polymer by this reaction are described in JP-A No. 2004-18831.
また本発明により、上記Wittig反応、あるいはWittig−Horner反応等を利用して、ベンゾジチオフェンにさらに新たな官能基を導入する事が容易に可能である。 Further, according to the present invention, it is possible to easily introduce a new functional group into benzodithiophene using the Wittig reaction or Wittig-Horner reaction.
次に本発明の式(I)及び(II)で表される化合物についてさらに詳細に説明する。
本発明において、「芳香族炭素水素あるいは芳香族複素環基」としては単環基、多環基(縮合多環基、非縮合多環基)の何れでもよく、一例としてベンゼン、ナフタレン、ビフェニル、ターフェニル、ピレン、フルオレン、9,9−ジメチルフルオレン、アズレン、アントラセン、トリフェニレン、クリセン、9−ベンジリデンフルオレン、5H−ジベンゾ[a,d]シクロヘプテン、トリフェニルアミン、チオフェン、ベンゾチオフェン、ジチエニルベンゼン、フラン、ベンゾフラン、カルバゾール、等の一価基または二価基が挙げられ、これらは置換もしくは無置換のアルキル基またはアルコキシ基を置換基として有していてもよい。
Next, the compounds represented by formulas (I) and (II) of the present invention will be described in more detail.
In the present invention, the “aromatic carbon hydrogen or aromatic heterocyclic group” may be either a monocyclic group or a polycyclic group (a condensed polycyclic group or a non-condensed polycyclic group), and examples thereof include benzene, naphthalene, biphenyl, Terphenyl, pyrene, fluorene, 9,9-dimethylfluorene, azulene, anthracene, triphenylene, chrysene, 9-benzylidenefluorene, 5H-dibenzo [a, d] cycloheptene, triphenylamine, thiophene, benzothiophene, dithienylbenzene, Examples thereof include monovalent groups or divalent groups such as furan, benzofuran, and carbazole, and these may have a substituted or unsubstituted alkyl group or alkoxy group as a substituent.
本明細書中、置換もしくは無置換のアルキル基とは、炭素数が1〜25の直鎖、分岐鎖又は環状のアルキル基であり、これらのアルキル基は更にハロゲン原子(特にフッ素原子)、シアノ基、フェニル基又は、直鎖あるいは分岐したアルキル基で置換されたフェニル基を含有してもよい。具体的には、メチル基、エチル基、n−プロピル基、i−プロピル基、t−ブチル基、s−ブチル基、n−ブチル基、i−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、3,7−ジメチルオクチル基、2−エチルヘキシル基、トリフルオロメチル基、2−シアノエチル基、ベンジル基、4−クロロベンジル基、4−メチルベンジル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
また、置換もしくは無置換のアルコキシ基である場合は、上記アルキル基の結合位に酸素原子を挿入してアルコキシ基としたものが具体例として挙げられる。
In the present specification, a substituted or unsubstituted alkyl group is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, and these alkyl groups are further halogen atoms (particularly fluorine atoms), cyano. A phenyl group substituted with a group, a phenyl group, or a linear or branched alkyl group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, Octyl, nonyl, decyl, undecyl, dodecyl, 3,7-dimethyloctyl, 2-ethylhexyl, trifluoromethyl, 2-cyanoethyl, benzyl, 4-chlorobenzyl, 4-methyl A benzyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.
In the case of a substituted or unsubstituted alkoxy group, specific examples include an alkoxy group formed by inserting an oxygen atom into the bonding position of the alkyl group.
これら置換基は同一のものを複数導入してもよく、また、異なる複数の基を導入してもよい。また、これらのアルキル基、及びアルコキシ基はさらにハロゲン原子、シアノ基、アリール基、ヒドロキシル基、カルボキシル基または、炭素数1〜12の直鎖、分岐鎖もしくは環状のアルキル基、アルコキシ基あるいはアルキルチオ基で置換されたアリール基を含有していてもよい。 A plurality of the same substituents may be introduced, or a plurality of different groups may be introduced. In addition, these alkyl groups and alkoxy groups are further halogen atoms, cyano groups, aryl groups, hydroxyl groups, carboxyl groups, linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, alkoxy groups or alkylthio groups. An aryl group substituted with may be contained.
以下に実施例により、本発明を更に具体的に説明するが、本発明は、これら実施例によって制限されるものではない。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
(化合物1の合成)
ヘキシルベンゾジチオフェン(Journal of Organic Chemistry,32,3093,1967.に従って合成した)11.00g(40.08mmol)を1Lの四つ口フラスコに入れ系内を窒素置換した後、乾燥ジエチルエーテル440mlを入れ、0℃に冷却した。ここにn-ブチルリチウム1.56Minヘキサン 77ml(120.2mmol)をゆっくりと滴下し、滴下終了後室温で1.5時間撹拌した。再び0℃に冷却し、乾燥DMF29.3ml(400mmol)を加えて0.5時間撹拌した。反応溶液を希塩酸、飽和食塩水の順に洗浄し、無水硫酸ナトリウムで乾燥した後、溶媒を留去した。残渣をカラムクロマトグラフィーにより精製し、ジアルデヒドを10.01g(30.28mmol)得た(収率76%、融点82−83℃)。
(Synthesis of Compound 1)
Hexyl benzodithiophene (synthesized according to Journal of Organic Chemistry, 32, 3093, 1967.) 11.00 g (40.08 mmol) was placed in a 1 L four-necked flask and the system was purged with nitrogen, and then 440 ml of dry diethyl ether was added. And cooled to 0 ° C. 77 ml (120.2 mmol) of n-butyllithium 1.56Min hexane was slowly added dropwise thereto, and the mixture was stirred at room temperature for 1.5 hours after completion of the dropwise addition. The mixture was cooled again to 0 ° C., 29.3 ml (400 mmol) of dry DMF was added, and the mixture was stirred for 0.5 hours. The reaction solution was washed with diluted hydrochloric acid and saturated brine in that order and dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was purified by column chromatography to obtain 10.1 g (30.28 mmol) of dialdehyde (yield 76%, melting point 82-83 ° C.).
上記操作で得られたジアルデヒド7.01g(21.20mmol)を容量500mlの四つ口フラスコに入れ、系内を窒素置換した。エタノール150ml及びTHF70mlを入れた後、0℃に冷却し、水素化ホウ素ナトリウム2.01g(53mmol)を少しずつ加えた。全量を加えた後、室温で20分撹拌した。再び0℃に冷却し、1Mの塩酸およそ60mlをゆっくりと加えた。エタノールを減圧留去した後、酢酸エチルを加え、水、飽和食塩水の順で洗浄した。無水硫酸ナトリウムで乾燥した後、溶媒を減圧留去し、目的のビスヒドロキシメチル体6.96g(20.81mmol)を得た(収率99%、融点125−127℃)。この式を下記式(17)に示す。 7.01 g (21.20 mmol) of dialdehyde obtained by the above operation was placed in a four-necked flask with a capacity of 500 ml, and the system was purged with nitrogen. After adding 150 ml of ethanol and 70 ml of THF, the mixture was cooled to 0 ° C., and 2.01 g (53 mmol) of sodium borohydride was added little by little. After the entire amount was added, the mixture was stirred at room temperature for 20 minutes. It was cooled again to 0 ° C. and approximately 60 ml of 1M hydrochloric acid was slowly added. Ethanol was distilled off under reduced pressure, ethyl acetate was added, and the mixture was washed with water and then saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 6.96 g (20.81 mmol) of the desired bishydroxymethyl compound (yield 99%, melting point 125-127 ° C.). This formula is shown in the following formula (17).
得られたビスヒドロキシメチル体の1H NMRスペクトル(400MHz,CDCl3,TMS)を図1に、IRスペクトル(窓材としてKBr使用)を図2に、それぞれ示す。 FIG. 1 shows the 1 H NMR spectrum (400 MHz, CDCl 3 , TMS) of the obtained bishydroxymethyl compound, and FIG. 2 shows the IR spectrum (using KBr as the window material).
(化合物2の合成)
実施例1で得られたビスヒドロキシメチル体6.95g(20.78mmol)を容量200mlの四つ口フラスコに入れ、系内を窒素置換した。1,4−ジオキサン30ml及び塩化チオニル4.2ml(58.18mmol)を加えた後、50℃に加熱して4.5時間撹拌した。0℃に冷却した後、少量のジエチルエーテルを加えて希釈し、飽和炭酸水素ナトリウム水溶液を発泡しなくなるまでゆっくりと加えた。ジエチルエーテルで抽出した後、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を減圧留去し、目的のビスクロロメチル体を7.64g(20.57mmol)得た(収率99% 黄色粘稠液体)。この式を(18)に示す。
(Synthesis of Compound 2)
6.95 g (20.78 mmol) of the bishydroxymethyl compound obtained in Example 1 was placed in a 200 ml four-necked flask, and the system was purged with nitrogen. After adding 30 ml of 1,4-dioxane and 4.2 ml (58.18 mmol) of thionyl chloride, the mixture was heated to 50 ° C. and stirred for 4.5 hours. After cooling to 0 ° C., a small amount of diethyl ether was added for dilution, and a saturated aqueous sodium hydrogen carbonate solution was slowly added until no foaming occurred. After extraction with diethyl ether, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 7.64 g (20.57 mmol) of the desired bischloromethyl compound (yield 99% yellow viscous liquid). This equation is shown in (18).
得られた化合物の1H NMRスペクトル(400MHz,CDCL3,TMS)を図3に、IRスペクトル(KBr)を図4に、それぞれ示す。 The 1 H NMR spectrum (400 MHz, CDCL 3 , TMS) of the obtained compound is shown in FIG. 3, and the IR spectrum (KBr) is shown in FIG.
実施例2で得られたビスクロロメチル体7.00g(18.85mmol)及び、亜リン酸トリエチル14.3mlを300ml四つ口フラスコに入れ、135℃に加熱した。135℃で5時間撹拌した後、亜りん酸トリエチルを減圧留去した。残渣をカラムクロマトグラフィーにより精製し、目的のリン化合物を3.04g(5.29mmol)得た。(収率28%、黄色粘稠液体)。この式を(19))に示す。 7.00 g (18.85 mmol) of the bischloromethyl product obtained in Example 2 and 14.3 ml of triethyl phosphite were placed in a 300 ml four-necked flask and heated to 135 ° C. After stirring at 135 ° C. for 5 hours, triethyl phosphite was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 3.04 g (5.29 mmol) of the target phosphorus compound. (Yield 28%, yellow viscous liquid). This equation is shown in (19).
得られた化合物の1H NMRスペクトル(400MHz,CDCl3,TMS)を図5に、IRスペクトル(neat,NaCl)を図6に、それぞれ示す。 The 1 H NMR spectrum (400 MHz, CDCl 3 , TMS) of the obtained compound is shown in FIG. 5, and the IR spectrum (neat, NaCl) is shown in FIG.
[重合体の合成例]
実施例3で得られたリン化合物1.522g(2.648mmol)及び、上記ジアルデヒド0.848g(2.648mmol)を、容量200mlの四つ口フラスコに入れ、系内を窒素置換した。乾燥THF80ml及び、ベンズアルデヒド14.05mg(0.132mmol)を加えた。この溶液にカリウム−ブトキシドの1M THF溶液8mlを滴下し、滴下終了後2時間攪拌した。さらに、ベンジルホスホン酸ジエチル60.5mg(0.265mmol)を加えて1時間攪拌した。反応溶液を水に注ぎ、析出した固体を濾過し、1.107gの重合体1を得た。粗収量率71%。さらにジクロロメタン及びメタノールから3回再沈精製し、赤色の粉末として0.624gの重合体1を得た(収率40%)。この式を下記式(20)に示す。
[Polymer synthesis example]
1.522 g (2.648 mmol) of the phosphorus compound obtained in Example 3 and 0.848 g (2.648 mmol) of the dialdehyde were placed in a four-necked flask having a capacity of 200 ml, and the system was purged with nitrogen. 80 ml of dry THF and 14.05 mg (0.132 mmol) of benzaldehyde were added. To this solution, 8 ml of 1M THF solution of potassium butoxide was added dropwise, and the mixture was stirred for 2 hours after completion of the addition. Furthermore, 60.5 mg (0.265 mmol) of diethyl benzylphosphonate was added and stirred for 1 hour. The reaction solution was poured into water, and the precipitated solid was filtered to obtain 1.107 g of the
得られた重合体の元素分析値を下記表1に示し、またこのIRスペクトル(NaClキャスト膜)を図7に示す。 The elemental analysis values of the obtained polymer are shown in Table 1 below, and the IR spectrum (NaCl cast film) is shown in FIG.
本発明によって、有機重合体型の半導体の原料を提供でき、この原料の提供によって、CVDなどの真空系での重合体の合成の可能性あるいは成膜化による薄膜化の可能性も生まれ、有機EL素子分野など多方面に渡る有機(半導体)デバイス応用研究を加速させる素材を提供可能となった。 According to the present invention, a raw material for an organic polymer type semiconductor can be provided. By providing this raw material, the possibility of synthesizing a polymer in a vacuum system such as CVD or the possibility of forming a thin film by forming a film is obtained. It has become possible to provide materials that accelerate organic (semiconductor) device application research in various fields such as the element field.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005294967A JP4889085B2 (en) | 2005-10-07 | 2005-10-07 | Benzodithiophene compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005294967A JP4889085B2 (en) | 2005-10-07 | 2005-10-07 | Benzodithiophene compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2007099736A true JP2007099736A (en) | 2007-04-19 |
JP4889085B2 JP4889085B2 (en) | 2012-02-29 |
Family
ID=38027016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005294967A Expired - Fee Related JP4889085B2 (en) | 2005-10-07 | 2005-10-07 | Benzodithiophene compounds |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4889085B2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007112878A (en) * | 2005-10-19 | 2007-05-10 | Ricoh Co Ltd | Benzodithiophene polymer |
JP2008277369A (en) * | 2007-04-26 | 2008-11-13 | Mitsui Chemicals Inc | Organic transistor |
JP2008300753A (en) * | 2007-06-04 | 2008-12-11 | Mitsui Chemicals Inc | Organic transistor |
JP2008300752A (en) * | 2007-06-04 | 2008-12-11 | Mitsui Chemicals Inc | Organic transistor |
WO2009113194A1 (en) * | 2008-03-10 | 2009-09-17 | 山本化成株式会社 | Organic transistor |
JP2010126480A (en) * | 2008-11-27 | 2010-06-10 | Wakayama Univ | Benzodithiophene-based compound, and composition and organic electroluminescent device containing the same compound |
JP2011526631A (en) * | 2008-07-02 | 2011-10-13 | ビーエーエスエフ ソシエタス・ヨーロピア | Poly (5,5'-bis (thiophen-2-yl) -benzo [2,1-b; 3,4-b '] dithiophene) and method for its use as a high performance solution capable of processing semiconductor polymers |
US8294144B2 (en) | 2007-03-23 | 2012-10-23 | Yamamoto Chemicals, Inc. | Organic transistor |
JP2013523931A (en) * | 2010-03-31 | 2013-06-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Fused ring dithiophene copolymer |
-
2005
- 2005-10-07 JP JP2005294967A patent/JP4889085B2/en not_active Expired - Fee Related
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007112878A (en) * | 2005-10-19 | 2007-05-10 | Ricoh Co Ltd | Benzodithiophene polymer |
JP4712514B2 (en) * | 2005-10-19 | 2011-06-29 | 株式会社リコー | Benzodithiophene polymer |
US8294144B2 (en) | 2007-03-23 | 2012-10-23 | Yamamoto Chemicals, Inc. | Organic transistor |
JP2008277369A (en) * | 2007-04-26 | 2008-11-13 | Mitsui Chemicals Inc | Organic transistor |
JP2008300753A (en) * | 2007-06-04 | 2008-12-11 | Mitsui Chemicals Inc | Organic transistor |
JP2008300752A (en) * | 2007-06-04 | 2008-12-11 | Mitsui Chemicals Inc | Organic transistor |
WO2009113194A1 (en) * | 2008-03-10 | 2009-09-17 | 山本化成株式会社 | Organic transistor |
JP2011526631A (en) * | 2008-07-02 | 2011-10-13 | ビーエーエスエフ ソシエタス・ヨーロピア | Poly (5,5'-bis (thiophen-2-yl) -benzo [2,1-b; 3,4-b '] dithiophene) and method for its use as a high performance solution capable of processing semiconductor polymers |
JP2010126480A (en) * | 2008-11-27 | 2010-06-10 | Wakayama Univ | Benzodithiophene-based compound, and composition and organic electroluminescent device containing the same compound |
JP2013523931A (en) * | 2010-03-31 | 2013-06-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Fused ring dithiophene copolymer |
Also Published As
Publication number | Publication date |
---|---|
JP4889085B2 (en) | 2012-02-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4889085B2 (en) | Benzodithiophene compounds | |
WO2006109895A1 (en) | Thiophene compound having phosphoric ester and process for producing the same | |
JP5229520B2 (en) | Novel benzodithiophene polymers | |
JP5387935B2 (en) | π-conjugated polymer | |
JP2007502251A (en) | Monomers, oligomers, and polymers of 2-functionalized and 2,7-difunctionalized carbazoles | |
CN107151312B (en) | A kind of indeno based conjugated polymers laser gain material and preparation method and application | |
JP4712514B2 (en) | Benzodithiophene polymer | |
US8299272B2 (en) | Process for production of fused ring compound | |
US20020041976A1 (en) | Novel compounds and their manufacture and use | |
WO2013108894A1 (en) | Fulvalene compound and method for producing same, fulvalene polymer, and solar cell material and organic transistor material | |
KR101117775B1 (en) | Composition for electron acceptor composition, method for preparing the same, photoelectric film comprising the same, and photoelectric device comprising the same | |
JP2009215425A (en) | pi-CONJUGATED ELECTRONIC POLYARYLENE ETHYNYLENE HAVING DINAPHTHOFURAN UNIT, AND METHOD FOR PRODUCING THE SAME | |
Wang et al. | Synthesis and characterization of a partial-conjugated hyperbranched poly (p-phenylene vinylene)(HPPV) | |
JP5391386B2 (en) | Bisphenazacillin compound, method for producing bisphenazacillin compound, organic thin film transistor using bisphenazacillin compound | |
KR100374018B1 (en) | Highly efficient blue and greenish-blue light-emitting polymer, producing method thereof, and EL device using the polymer | |
JP2005240001A (en) | New arylamine polymer | |
JP5105938B2 (en) | Polymer and process for producing the same | |
JP6319979B2 (en) | Boron-containing compound and boron-containing polymer | |
JP6596109B2 (en) | Boron-containing compound and boron-containing polymer | |
JP4160142B2 (en) | Di-p-tolyldialkylsilane derivative, light-emitting polymer comprising the same, and method for producing the same | |
JP4546904B2 (en) | Novel arylamine polymer | |
JP5770642B2 (en) | Compound having trimethylene structure, polymer compound containing unit having trimethylene structure, and reactive compound having trimethylene structure | |
Ghase et al. | Alkyl and allyl substituted polydibenzofluorene: blue emitters for future display applications | |
JP2005213228A (en) | New dialdehyde compound and arylamine polymer | |
JP2010053093A (en) | New tin compound having benzobisthiazole skeleton |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080912 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20080919 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110914 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110915 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111114 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111208 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111212 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4889085 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141222 Year of fee payment: 3 |
|
LAPS | Cancellation because of no payment of annual fees |