JP2008162967A - Method for synthesizing asymmetric bis (terpyridine) compound - Google Patents
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本発明は、金属イオンとの錯形成によるハイブリッドポリマーがエレクトロクロミック材料として期待されている非対称ビス（ターピリジル）ベンゼン誘導体をはじめとする各種の非対称型ビス(ターピリジン)化合物の合成方法に関するものである。 The present invention relates to a method for synthesizing various asymmetric bis (terpyridine) compounds including asymmetric bis (terpyridyl) benzene derivatives for which hybrid polymers by complex formation with metal ions are expected as electrochromic materials.
従来より、ビス（ターピリジル）ベンゼン誘導体は金属イオンと錯形成してハイブリッドポリマーとなり、このものは優れたエレクトロクロミック特性を示すことが知られている。このため、このハイブリッドポリマーは、電子ペーパー等の表示材料として将来の技術展開が期待されている。そして、表示デバイスへの応用のためには、エレクトロクロミックのマルチカラー化が望まれ、そのための検討も進められている。 Conventionally, bis (terpyridyl) benzene derivatives are complexed with metal ions to form hybrid polymers, which are known to exhibit excellent electrochromic properties. For this reason, this hybrid polymer is expected to develop in the future as a display material such as electronic paper. For application to display devices, electrochromic multi-coloring is desired, and studies for that purpose are underway.
しかしながら、ビス（ターピリジル）ベンゼン誘導体をはじめとするビス(ターピリジ
ン)化合物についての従来の知見（非特許文献１−２）によれば、その合成方法は極めて
限られた構造と官能基の導入しか可能でなく、また、非対称型の分子構造を持つものとすることが困難であった。
However, according to conventional knowledge about bis (terpyridine) compounds including bis (terpyridyl) benzene derivatives (Non-Patent Document 1-2), the synthesis method can only introduce very limited structures and functional groups. In addition, it was difficult to have an asymmetric molecular structure.
このため、マルチカラー化を可能とするための分子構造と官能基の設計とその合成の自由度に乏しく、技術的応用展開のための大きな障害となっていた。
本発明は、上記のとおりの背景から、従来技術の問題点を解消し、ハイブリッドポリマーのマルチカラー化を可能ともするために、分子構造と官能基の設計とその合成が自由度が大きく、複雑な多段階反応を必要としない、非対称型ビス−ターピリジン化合物の新しい合成方法を提供することを課題としている。 From the background described above, the present invention eliminates the problems of the prior art and enables the multi-coloring of the hybrid polymer, so that the design and synthesis of the molecular structure and functional groups are highly flexible and complicated. It is an object of the present invention to provide a new method for synthesizing asymmetric bis-terpyridine compounds that does not require a multistage reaction.
本発明の非対称型ビス(ターピリジン)化合物の合成方法は以下のことを特徴としている。
第１： 次式（１）
The synthesis method of the asymmetric bis (terpyridine) compound of the present invention is characterized by the following.
1: The following formula (1)
（式中の２つＲ1は、各々、同一または別異に、水素原子または置換基を示し、Ａ1は炭化水素基を示し、Ｘはハロゲン原子を示す。）
で表されるターピリジン化合物を、次式（２）
(Two R 1 s in the formula are the same or different and each represents a hydrogen atom or a substituent, A 1 represents a hydrocarbon group, and X represents a halogen atom.)
A terpyridine compound represented by the following formula (2)
（式中のＲa、Ｒb、Ｒc、Ｒdは各々、炭化水素基を示し、ＲaとＲb、ＲcとＲdは相互に結合していてもよい。）
で表されるホウ素化合物の存在下にカップリング反応させた後、さらに次式（３）
(In the formula, R a , R b , R c and R d each represents a hydrocarbon group, and R a and R b , and R c and R d may be bonded to each other.)
After the coupling reaction in the presence of a boron compound represented by the following formula (3)
（式中の２つＲ2は前記Ｒ1と別異に、かつ、各々、同一または別異に水素原子または置換基を示し、Ａ2はＡ1と同一または別異に、炭化水素基を示し、Ｘはハロゲン原子を示す。）
で表されるターピリジン化合物とカップリング反応させて、次式（４）
(In the formula, two R 2 s are different from R 1 and each represents the same or different hydrogen atom or substituent, and A 2 is the same or different from A 1 and represents a hydrocarbon group. X represents a halogen atom.)
And a terpyridine compound represented by the following formula (4):
（前記のとおり、式中のＡ1およびＡ2は、同一または別異に、各々、炭化水素基を示し、Ｒ1およびＲ2は互いに別異に、各々、水素原子または置換基を示す。）
で表される化合物を合成することを特徴とする。
第２： 第1の発明において、カップリング反応は、パラジウム錯体化合物と塩基の共存
下に反応させることを特徴とする。
第３： 第1又は第2の発明において、式（１）の符号Ｒ1および式（３）の符号Ｒ2の置換基は、各々、炭化水素基、アルコキシ基、アミノ基、カルボニル基、カルボン酸エステル基、シアノ基、ニトロ基、または、これらを有する炭化水素基であることを特徴とする。第４： 第1から第3のいずれかの発明において、式（１）の符号Ａ1および式（３）のＡ2の炭化水素基は、芳香族基または複素環基であることを特徴とする。
(As described above, A 1 and A 2 in the formula are the same or different and each represents a hydrocarbon group, and R 1 and R 2 are different from each other and each represents a hydrogen atom or a substituent. )
The compound represented by these is synthesized.
Second: In the first invention, the coupling reaction is characterized in that the reaction is carried out in the presence of a palladium complex compound and a base.
Third: In the first or second invention, the substituents represented by the symbol R 1 in the formula (1) and the symbol R 2 in the formula (3) are a hydrocarbon group, an alkoxy group, an amino group, a carbonyl group, a carboxylic group, respectively. It is an acid ester group, a cyano group, a nitro group, or a hydrocarbon group having these. Fourth: In any one of the first to third inventions, the hydrocarbon group of the symbol A 1 in the formula (1) and the A 2 in the formula (3) is an aromatic group or a heterocyclic group, To do.
上記のとおりの本発明の合成方法によれば、異なる２種類のターピリジン化合物を原料とすることで非対称型のビス(ターピリジン)化合物を合成することができる。しかもまた、本発明の方法によれば、ピリジン環には各種の官能置換基を導入したものとすることができる。これによって、ビス−ターピリジン化合物の分子構造や、官能基の導入の選択幅は拡がって、設計そして合成の自由度は大きく向上する。ビス−ターピリジン化合物からのハイブリッドポリマーのマルチカラー化へも大きく前進することになる。 According to the synthesis method of the present invention as described above, an asymmetric bis (terpyridine) compound can be synthesized by using two different types of terpyridine compounds as raw materials. Moreover, according to the method of the present invention, various functional substituents can be introduced into the pyridine ring. As a result, the molecular structure of the bis-terpyridine compound and the selection range for the introduction of functional groups are expanded, and the degree of freedom in design and synthesis is greatly improved. A major advance will also be made to multicolorization of hybrid polymers from bis-terpyridine compounds.
しかも本発明の方法においては、複雑な多段階反応を必要とせず、良好な効率での合成反応が実現されることになる。 Moreover, in the method of the present invention, a complicated multistage reaction is not required, and a synthesis reaction with good efficiency is realized.
本発明の実施の形態について以下に説明する。 Embodiments of the present invention will be described below.
本発明では、異なる２種類の原料化合物であるターピリジン化合物を用いて非対称型の
ビス(ターピリジン)化合物を合成するものであり、このようなターピリジン化合物としては、一般的には前記式の式（１）および式（３）により表すことができる。
In the present invention, an asymmetric bis (terpyridine) compound is synthesized by using a terpyridine compound which is two different raw material compounds. Such a terpyridine compound is generally represented by the formula (1) ) And formula (3).
この式（１）のピリジン環における符号Ｒ1および式（３）のピリジン環における符号
Ｒ2は、各々、別異の、水素原子または許容される数の官能置換基を示している。そして
、式（１）の２つの符号Ｒ1は、各々、同一または別異の水素原子または任意の置換基で
あり、式（３）の２つの符号Ｒ2についても、各々、同一または別異の水素原子または任
意の置換基である。置換基としては、たとえば、脂肪族の炭素数１〜１６の範囲のアルキル基やアルケニル基、あるいはシクロアルキル基、フェニル基等のアリール基、ヒドロキシ（ＯＨ）基、炭素数１〜１６の範囲の脂肪族炭化水素基を有するアルコキシ基、アミノ（ＮＨ2）基、炭素数１〜１６の範囲の脂肪族炭化水素基を有するモノ−またはジ−置換
アミノ基、アルデヒド（ＣＨＯ）基または炭素数１〜１６の範囲の脂肪族炭化水素基を有するケトン基あるいはカルボン酸エステル基、シアノ基、ニトロ基、さらには以上の置換基を結合する炭化水素基等の各種のものであってよい。これらの置換基は、式（１）または式（３）において任意のピリジン環構成炭素原子に１または２以上結合していてもよい。
The symbol R 1 in the pyridine ring of the formula (1) and the symbol R 2 in the pyridine ring of the formula (3) each represent a different hydrogen atom or an allowable number of functional substituents. The two symbols R 1 in the formula (1) are the same or different hydrogen atoms or arbitrary substituents, respectively, and the two symbols R 2 in the formula (3) are also the same or different. A hydrogen atom or an optional substituent. Examples of the substituent include, for example, an aliphatic alkyl group or alkenyl group having 1 to 16 carbon atoms, or an aryl group such as a cycloalkyl group or a phenyl group, a hydroxy (OH) group, or a group having 1 to 16 carbon atoms. An alkoxy group having an aliphatic hydrocarbon group, an amino (NH 2 ) group, a mono- or di-substituted amino group having an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aldehyde (CHO) group or a carbon number of 1 Various groups such as a ketone group having a aliphatic hydrocarbon group in the range of ˜16, a carboxylic acid ester group, a cyano group, a nitro group, and a hydrocarbon group to which the above substituents are bonded may be used. One or more of these substituents may be bonded to any pyridine ring constituting carbon atom in the formula (1) or the formula (3).
式（１）の符号Ａ1および式（３）の符号Ａ2は、各々、同一または別異の、スペーサー分子鎖としての炭化水素基を示している。スペーサー分子鎖としての符号Ａ1および符号
Ａ2は、脂肪族、脂環族、芳香族、あるいは複素環の各種の炭化水素基であってよく、た
とえば、エレクトロクロミック材料としてのハイブリッドポリマーの合成原料としては、フェニル基、ビフェニル基、トリル基、ベンジル基等の各種のアリール基や複素環基であることが好適に考慮される。
The symbol A 1 in the formula (1) and the symbol A 2 in the formula (3) each represent the same or different hydrocarbon group as a spacer molecular chain. The symbols A 1 and A 2 as spacer molecular chains may be aliphatic, alicyclic, aromatic, or heterocyclic hydrocarbon groups, for example, raw materials for synthesizing hybrid polymers as electrochromic materials. As such, various aryl groups such as phenyl group, biphenyl group, tolyl group, and benzyl group, and heterocyclic groups are preferably considered.
式（１）および式（３）の符号Ｘのハロゲン原子としては、塩素原子、臭素原子またはヨウ素原子が例示される。 Examples of the halogen atom represented by the symbol X in the formulas (1) and (3) include a chlorine atom, a bromine atom and an iodine atom.
本発明の合成方法によれば、まず、前記式（１）で表されるターピリジン化合物と前記式（２）で表されるホウ素化合物とをカップリング反応させた後、さらに前記式（３）で表されるターピリジン化合物とカップリング反応させて、前記式（４）で表される非対称のビス(ターピリジン)化合物を合成している。ここで、式（２）のホウ素化合物の符号Ｒa、Ｒb、Ｒc、Ｒdは、各々、炭化水素基を示し、ＲaとＲb、ＲcとＲdは相互に結合して、ホウ素原子と共に環を形成していてもよい。このホウ素化合物については、原料のターピリジン化合物に対して、通常は、モル比で１．０〜２．０倍使用することが考慮される。 According to the synthesis method of the present invention, first, a terpyridine compound represented by the formula (1) and a boron compound represented by the formula (2) are subjected to a coupling reaction, and then the formula (3). The asymmetric bis (terpyridine) compound represented by the formula (4) is synthesized by a coupling reaction with the represented terpyridine compound. Here, the symbols R a , R b , R c , R d of the boron compound of the formula (2) each represent a hydrocarbon group, and R a and R b , R c and R d are bonded to each other. A ring may be formed with a boron atom. With respect to this boron compound, it is usually considered to be used in a molar ratio of 1.0 to 2.0 times with respect to the starting terpyridine compound.
また、前記式（１）で表されるターピリジン化合物と前記式（２）で表されるホウ素化合物とのカップリング反応、およびその後の前記式（３）で表されるターピリジン化合物とのカップリング反応では、パラジウム（Ｐｄ）の錯体化合物と塩基を用いることが有効である。パラジウム錯体化合物は、たとえばＰｄＣｌ2（ＰＰｈ3）2やＰｄＣｌ2（ｄｐｐｆ）のような０価のＰｄ錯体が好適なものとして考慮される。塩基については、たとえばＬｉ、Ｎａ、Ｋ、Ｃｓのアルカリ金属の水酸化物、炭酸塩、炭酸水素塩、有機酸塩、フッ化物等が好ましいものとして例示される。より具体的には、ＫＯＨ、ＮａＯＨ、ＬｉＯＨ、Ｋ2ＣＯ3、ＮａＨＣＯ3、ＫＨＣＯ3、ＫＯＡｃ、ＫＦ等である。 In addition, a coupling reaction between the terpyridine compound represented by the formula (1) and the boron compound represented by the formula (2), and a subsequent coupling reaction with the terpyridine compound represented by the formula (3) Then, it is effective to use a complex compound of palladium (Pd) and a base. As the palladium complex compound, for example, a zero-valent Pd complex such as PdCl 2 (PPh 3 ) 2 or PdCl 2 (dppf) is considered suitable. As the base, for example, alkali metal hydroxides of Li, Na, K, and Cs, carbonates, hydrogen carbonates, organic acid salts, fluorides, and the like are exemplified as preferable examples. More specifically, KOH, NaOH, LiOH, K 2 CO 3 , NaHCO 3 , KHCO 3 , KOAc, KF and the like.
パラジウム錯体化合物、そして塩基の使用割合は、それぞれの原料のターピリジン化合物に対して、各々、モル比で、１×１０-2〜３×１０-1倍、５×１０-1〜５倍の範囲とすることが好ましい。 The use ratio of the palladium complex compound and the base is in the range of 1 × 10 −2 to 3 × 10 −1 times and 5 × 10 −1 to 5 times in molar ratio with respect to the terpyridine compound of each raw material. It is preferable that
反応には溶媒を用いることができる。たとえばＤＭＳＯ、ＤＭＦ、ＴＨＦ、アルコール、水、ジオキサン、トルエン、ベンゼン等の１種または２種以上である。ただ、極性溶媒
を用いることがより好ましい。
A solvent can be used for the reaction. For example, one or more of DMSO, DMF, THF, alcohol, water, dioxane, toluene, benzene and the like. However, it is more preferable to use a polar solvent.
反応は、大気もしくは不活性ガス雰囲気下において、常圧、もしくは減圧または加圧下とすることができる。大気中で行うことがより簡便であり、反応温度としては、６×１０℃〜１２×１０℃の範囲とすることがより好ましい。 The reaction can be under normal pressure, reduced pressure, or increased pressure in the atmosphere or an inert gas atmosphere. It is easier to carry out in the atmosphere, and the reaction temperature is more preferably in the range of 6 × 10 ° C. to 12 × 10 ° C.
そこで以下に実施例を示し、さらに詳しく説明する。もちろん、以下の例によって発明が限定されることはない。 Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.
１（１００ｍｇ，０．２５８ｍｍｏｌ）を５ｍＬ ＤＭＳＯに溶かした溶液に、２（７８ｍｇ，０．３０９ｍｍｏｌ）、ＫＯＡｃ（７６ｍｇ，０．７７３ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2（９．０ｍｇ，０．０１３ｍｍｏｌ）を加えた。１０分間脱気した後、８
０oＣで１２時間攪拌した。反応溶液をろ過し、ＣＨＣｌ3を加え希釈した。脱イオン水（１０ｍＬ）で５回洗浄し、ＭｇＳＯ4で乾燥させた。ボロン酸粗生成物（４９ｍｇ，０．
１１２ｍｍｏｌ）に、３（５０ｍｇ，０．１１２ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2（
４ｍｇ，０．００６ｍｍｏｌ）、Ｋ2ＣＯ3（４６ｍｇ，０．３３６ｍｍｏｌ）を６ｍＬ ＤＭＳＯに溶かした溶液を加えた。１０分間脱気した後、８０oＣで１８時間攪拌した。
反応溶液を室温まで冷却し、ろ過した。ろ液をＣＨＣｌ3で希釈し、脱イオン水で５回洗
浄した。ＭｇＳＯ4で乾燥し、ろ過、濃縮後、カラムクロマトグラフィー（Ａｌ2Ｏ3，ｂ
ａｓｉｃ）で目的物４を得た（４３ｍｇ（５７％），ｗｈｉｔｅ ｓｏｌｉｄ）。
In a solution of 1 (100 mg, 0.258 mmol) in 5 mL DMSO, 2 (78 mg, 0.309 mmol), KOAc (76 mg, 0.773 mmol), PdCl 2 (PPh 3 ) 2 (9.0 mg, 0.013 mmol) ) Was added. After degassing for 10 minutes, 8
Stir at 0 ° C. for 12 hours. The reaction solution was filtered and diluted by adding CHCl 3 . Washed 5 times with deionized water (10 mL) and dried over MgSO 4 . Boronic acid crude product (49 mg, 0.
112 mmol), 3 (50 mg, 0.112 mmol), PdCl 2 (PPh 3 ) 2 (
4 mg, 0.006 mmol) and a solution of K 2 CO 3 (46 mg, 0.336 mmol) in 6 mL DMSO were added. After degassing for 10 minutes, the mixture was stirred at 80 ° C. for 18 hours.
The reaction solution was cooled to room temperature and filtered. The filtrate was diluted with CHCl 3 and washed 5 times with deionized water. After drying over MgSO 4 , filtration and concentration, column chromatography (Al 2 O 3 , b
asic) to obtain the target compound 4 (43 mg (57%), white solid).
１（１００ｍｇ，０．２５８ｍｍｏｌ）を５ｍＬ ＤＭＦに溶かした溶液に、２（７８ｍｇ，０．３０９ｍｍｏｌ）、ＫＯＡｃ（７６ｍｇ，０．７７３ｍｍｏｌ）、ＰｄＣｌ2
（ｄｐｐｆ）（６３ｍｇ，０．０７７ｍｍｏｌ）を加えた。１０分間脱気した後、８０o
Ｃで１２時間攪拌した。反応溶液をろ過し、ＣＨＣｌ3で希釈した後、脱イオン水で５回
洗浄した。ＭｇＳＯ4で乾燥させ、ろ過、濃縮した。得られたボロン酸粗生成物（４９ｍ
ｇ，０．１１２ｍｍｏｌ）に、３（５０ｍｇ，０．１１２ｍｍｏｌ）、ＰｄＣｌ2（ＰＰ
ｈ3）2（４ｍｇ，０．００６ｍｍｏｌ）、Ｋ2ＣＯ3（４６ｍｇ，０．３３６ｍｍｏｌ）を６ｍＬ ＤＭＳＯに溶かして加えた。１０分間脱気した後、８０oＣで１８時間攪拌した
。反応終了後、室温まで冷却し、ろ過した。ろ液にＣＨＣｌ3を加え、脱イオン水で５回
洗浄した。ＭｇＳＯ4で乾燥させた後、ろ過し、濃縮した。カラムクロマトグラフィー（
Ａｌ2Ｏ3，ｂａｓｉｃ）で目的物４を単離した（３９ｍｇ５４％），ｗｈｉｔｅ ｓｌｉｇｈｔ ｒｅｄ ｓｏｌｉｄ）。
In a solution of 1 (100 mg, 0.258 mmol) in 5 mL DMF, 2 (78 mg, 0.309 mmol), KOAc (76 mg, 0.773 mmol), PdCl 2
(Dppf) (63 mg, 0.077 mmol) was added. 80 o after degassing for 10 minutes
Stir at C for 12 hours. The reaction solution was filtered, diluted with CHCl 3 and washed 5 times with deionized water. Dried over MgSO 4 , filtered and concentrated. The resulting boronic acid crude product (49 m
g, 0.112 mmol), 3 (50 mg, 0.112 mmol), PdCl 2 (PP
h 3 ) 2 (4 mg, 0.006 mmol) and K 2 CO 3 (46 mg, 0.336 mmol) were dissolved in 6 mL DMSO and added. After degassing for 10 minutes, the mixture was stirred at 80 ° C. for 18 hours. After completion of the reaction, it was cooled to room temperature and filtered. CHCl 3 was added to the filtrate and washed 5 times with deionized water. After drying over MgSO 4 , it was filtered and concentrated. Column chromatography (
The target product 4 was isolated with Al 2 O 3 (basic) (39 mg 54%) (white light red solid).
１（１００ｍｇ，０．２５８ｍｍｏｌ）を８ｍＬ ＤＭＳＯに溶かした溶液に、２（７２ｍｇ，０．２８３ｍｍｏｌ）、ＫＯＡｃ（７６ｍｇ，０．７７３ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2（９．０ｍｇ，０．０１３ｍｍｏｌ）を加えた。１０分間脱気した後、８
０oＣで１２時間攪拌した。その後、反応容器に８ｍＬ ＤＭＳＯを加えた後、Ｋ2ＣＯ3
（１０７ｍｇ，０．７７３ｍｍｏｌ）、３（１１５ｍｇ，０．２５８ｍｍｏｌ）、ｃａｔａｌｙｓｔ（５％ｍｏｌ）をさらに加えた。１２０oＣで２０時間攪拌し、室温まで冷却
した後、ＣＨＣｌ3で希釈し、ろ過した。ろ液を脱イオン水（３０ｍＬ）で５回洗浄し、
ＭｇＳＯ4で乾燥させた。ろ過、濃縮後、カラムクロマトグラフィー（Ａｌ2Ｏ3， ｂａ
ｓｉｃ）で目的物４を単離した（９９ｍｇ（５７％），ｗｈｉｔｅ ｓｏｌｉｄ）。
In a solution of 1 (100 mg, 0.258 mmol) in 8 mL DMSO, 2 (72 mg, 0.283 mmol), KOAc (76 mg, 0.773 mmol), PdCl 2 (PPh 3 ) 2 (9.0 mg, 0.013 mmol) ) Was added. After degassing for 10 minutes, 8
Stir at 0 ° C. for 12 hours. Thereafter, 8 mL DMSO was added to the reaction vessel, and then K 2 CO 3 was added.
(107 mg, 0.773 mmol), 3 (115 mg, 0.258 mmol) and catalyst (5% mol) were further added. The mixture was stirred at 120 ° C. for 20 hours, cooled to room temperature, diluted with CHCl 3 and filtered. Wash the filtrate 5 times with deionized water (30 mL),
Dried over MgSO 4 . After filtration and concentration, column chromatography (Al 2 O 3 , ba
sic) to isolate the target compound 4 (99 mg (57%), white solid).
１（５０ｍｇ，０．１２９ｍｍｏｌ）を４ｍＬ ＤＭＳＯに溶かした溶液に、２（３６ｍｇ，０．１４２ｍｍｏｌ）、ＫＯＡｃ（３８ｍｇ，０．３８６ｍｍｏｌ）、ＰｄＣｌ2
（ＰＰｈ3）2（５ｍｇ，０．００６ｍｍｏｌ）を加えた。１０分間脱気した後、８０oＣ
で８時間攪拌した。反応溶液に４ｍＬ ＤＭＳＯを加えた後、さらにＫ2ＣＯ3（５４ｍｇ，０．３８６ｍｍｏｌ）、５（５６ｍｇ，０．１２９ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2を加え、８０oＣで１６時間攪拌した。その後、室温まで冷却しＣＨＣｌ3で希釈した後
、脱イオン水（３０ｍＬ）で５回洗浄し、ＭｇＳＯ4で乾燥させた。溶液を濃縮後、カラ
ムクロマトグラフィー（Ａｌ2Ｏ3，ｂａｓｉｃ）で目的物６を単離した（５６ｍｇ（６５％），ｗｈｉｔｅ ｓｏｌｉｄ）。
In a solution of 1 (50 mg, 0.129 mmol) in 4 mL DMSO, 2 (36 mg, 0.142 mmol), KOAc (38 mg, 0.386 mmol), PdCl 2
(PPh 3 ) 2 (5 mg, 0.006 mmol) was added. 80 ° C after degassing for 10 minutes
For 8 hours. After adding 4 mL DMSO to the reaction solution, K 2 CO 3 (54 mg, 0.386 mmol), 5 (56 mg, 0.129 mmol) and PdCl 2 (PPh 3 ) 2 were further added and stirred at 80 ° C. for 16 hours. . After cooling to room temperature and diluting with CHCl 3 , it was washed 5 times with deionized water (30 mL) and dried over MgSO 4 . After concentration of the solution, the target compound 6 was isolated by column chromatography (Al 2 O 3 , basic) (56 mg (65%), white solid).
Claims (4)
で表されるターピリジン化合物を、次式（２）
で表されるホウ素化合物の存在下にカップリング反応させた後、さらに次式（３）
）
で表されるターピリジン化合物とカップリング反応させて、次式（４）
で表される化合物を合成することを特徴とする非対称型ビス(ターピリジン)化合物の合成方法。 The following formula (1)
A terpyridine compound represented by the following formula (2)
After the coupling reaction in the presence of a boron compound represented by the following formula (3)
)
And a terpyridine compound represented by the following formula (4):
A method for synthesizing an asymmetric bis (terpyridine) compound, which comprises synthesizing a compound represented by the formula:
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| WO2011096386A1 (en) | 2010-02-08 | 2011-08-11 | 独立行政法人物質・材料研究機構 | Smart window employing organic/metallic hybrid polymer, method for manufacturing smart window, and smart window system |
| WO2012093547A1 (en) | 2011-01-04 | 2012-07-12 | 独立行政法人物質・材料研究機構 | Electronic printable medium, electronic print device, and method for printing on electronic printable medium |
| WO2016150921A1 (en) | 2015-03-24 | 2016-09-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrochromic element with improved electrolyte layer |
| US9753347B2 (en) | 2012-01-30 | 2017-09-05 | National Institute For Materials Science | Electrochromic gel, method for producing the gel, method for controlling electronic printing and erasing on electrochromic gel, and stretchable display |
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| JP2003229579A (en) * | 2001-11-28 | 2003-08-15 | Konica Corp | Field effect transistor and manufacturing method therefor |
| JP2006504779A (en) * | 2002-11-06 | 2006-02-09 | ザ・ユニバーシティ・オブ・ホンコン | Electroluminescent metal supramolecules with terpyridine group |
| WO2005014566A1 (en) * | 2003-08-07 | 2005-02-17 | Bayer Pharmaceuticals Corporation | Benzofuran derivatives useful for treating hyper-proliferative disorders |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011096386A1 (en) | 2010-02-08 | 2011-08-11 | 独立行政法人物質・材料研究機構 | Smart window employing organic/metallic hybrid polymer, method for manufacturing smart window, and smart window system |
| WO2012093547A1 (en) | 2011-01-04 | 2012-07-12 | 独立行政法人物質・材料研究機構 | Electronic printable medium, electronic print device, and method for printing on electronic printable medium |
| US9753347B2 (en) | 2012-01-30 | 2017-09-05 | National Institute For Materials Science | Electrochromic gel, method for producing the gel, method for controlling electronic printing and erasing on electrochromic gel, and stretchable display |
| WO2016150921A1 (en) | 2015-03-24 | 2016-09-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrochromic element with improved electrolyte layer |
| DE102015104439A1 (en) | 2015-03-24 | 2016-09-29 | Bayerische Motoren Werke Aktiengesellschaft | Electrochromic element with improved electrolyte layer |
| DE102015104439B4 (en) | 2015-03-24 | 2019-02-21 | Bayerische Motoren Werke Aktiengesellschaft | Electrochromic element with improved electrolyte layer, process for its production, vehicle glazing and vehicle |
| US10268096B2 (en) | 2015-03-24 | 2019-04-23 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Electrochromic element with improved electrolyte layer |
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