JP2007131608A - New dysprosium derivative - Google Patents
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- JP2007131608A JP2007131608A JP2005354084A JP2005354084A JP2007131608A JP 2007131608 A JP2007131608 A JP 2007131608A JP 2005354084 A JP2005354084 A JP 2005354084A JP 2005354084 A JP2005354084 A JP 2005354084A JP 2007131608 A JP2007131608 A JP 2007131608A
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Abstract
Description
本発明は新規ジスプロシウム誘導体に関するもので、有機合成の属する分野、医療、エネルギー、機械、情報分野、および他の分野において要求されている磁性流体、磁性イオン液体を提供するものである。 The present invention relates to a novel dysprosium derivative, and provides a magnetic fluid and a magnetic ionic liquid required in the fields of organic synthesis, medicine, energy, machinery, information, and other fields.
イオン液体はイミダゾリウムイオン、ピリジニウムイオンなどの陽イオンと、ＢＦ４−、ＰＦ６−などの陰イオンから成る塩で、比較的低温で液体状態となる。その特徴としては蒸気圧がほとんどなく不揮発性、不燃性で、熱安定性が高く幅広い温度範囲で比較的低粘性の液体状態である。また、イオン伝導性が高いことなどが挙げられる。このように従来の液体と異なる特徴を有するイオン液体は、基礎研究は勿論のこと多方面での応用研究が活発に行われている。例えば、有機合成の分野では反応溶媒として利用が挙げられる。イオン液体はイオンのみから構成されており、反応溶媒として用いた場合、溶質はイオンのみに溶媒和され、通常の有機溶媒を用いた時と全く異なった環境下で反応が進行する。そのため、従来にない反応性を示すことが期待され、種々の有機合成への適用が試みられている。また、導電性が高く不揮発性、不燃性であるため、二次電池や色素増感型太陽電池の電解質などとしての応用が盛んに検討されている。The ionic liquid is a salt composed of a cation such as imidazolium ion or pyridinium ion and an anion such as BF 4 − or PF 6 − and is in a liquid state at a relatively low temperature. Its characteristics are that it has almost no vapor pressure, is non-volatile, non-flammable, has high thermal stability, and is in a liquid state having a relatively low viscosity over a wide temperature range. In addition, the ion conductivity is high. As described above, ionic liquids having characteristics different from those of conventional liquids are actively being studied in various fields as well as basic research. For example, it can be used as a reaction solvent in the field of organic synthesis. The ionic liquid is composed only of ions, and when used as a reaction solvent, the solute is solvated only with ions, and the reaction proceeds in an environment completely different from that when a normal organic solvent is used. For this reason, it is expected to exhibit unprecedented reactivity, and application to various organic syntheses has been attempted. In addition, since it has high conductivity and is non-volatile and nonflammable, its application as an electrolyte for secondary batteries and dye-sensitized solar cells has been actively studied.
上記のように様々な分野での応用研究がなされている一方で、種々のカチオン、アニオンを組み合わせ、新規イオン液体が合成され、新たな機能が発現している。近年、発明者らが報告した１−ブチル−３−メチルイミダゾリウムテトラクロロフェラートもそうしたイオン液体の一つである（非特許文献１）。このイオン液体は磁性を有しており、磁石に引き寄せられる。従来から知られている磁性流体はマグネタイトなどの強磁性体の超微粒子を液体中に分散させた流体で、一般に媒体となる液体、強磁性体の超微粒子、強磁性体の超微粒子を安定に分散させるための界面活性剤から構成される複合材料である。磁性流体は液体でありながら磁石に引き寄せられるという特異な性質を有しており、この性質を利用して多方面で実用に供されている。例えば、回転軸のシール、振動系のダンパー、傾斜センサー、角度センサーなどが挙げられ、その利用の範囲は広がりつつある。しかしながら、磁石に引き寄せられるのは磁性流体に分散している強磁性体の超微粒子で、そのため、磁場の下で偏析することが知られている。また、媒体の蒸発などの問題を有している。発明者らの開発した磁性イオン液体１−ブチル−３−メチルイミダゾリウムテトラクロロフェラートはこれらの諸問題を克服した新しい磁性流体として回転軸のシール、振動系のダンパー、傾斜センサーを始めとする多方面での応用が期待されている。 As described above, applied research in various fields has been conducted, and various cations and anions are combined to synthesize new ionic liquids and develop new functions. In recent years, 1-butyl-3-methylimidazolium tetrachloroferrate reported by the inventors is one of such ionic liquids (Non-patent Document 1). This ionic liquid has magnetism and is attracted to the magnet. A conventionally known magnetic fluid is a fluid in which ultrafine particles of ferromagnetic material such as magnetite are dispersed in a liquid. Generally, the medium, the ultrafine particles of ferromagnetic material, and the ultrafine particles of ferromagnetic material are stabilized. It is a composite material composed of a surfactant for dispersion. A magnetic fluid has a unique property of being attracted to a magnet while being a liquid, and is utilized in various fields by utilizing this property. For example, a rotary shaft seal, a vibration damper, a tilt sensor, an angle sensor, and the like can be cited, and the range of use is expanding. However, it is known that the ultrafine particles of ferromagnetic material dispersed in the magnetic fluid are attracted to the magnet, and therefore segregate under a magnetic field. In addition, there are problems such as evaporation of the medium. The magnetic ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate developed by the inventors is a new magnetic fluid that overcomes these problems, including a rotary shaft seal, vibration damper, and tilt sensor. Applications in various fields are expected.
しかしながら、従来の磁性流体は光を透過させることができず、また、１−ブチル−３−メチルイミダゾリウムテトラクロロフェラート等の磁性イオン液体は暗褐色に着色している。無色透明の磁性流体、磁性イオン液体は視覚的にも光化学的にも興味深い磁性材料であるが、いまだ得られていない。視覚性、可視光の透過性に優れた無色透明の磁性流体、磁性イオン液体が求められている。 However, conventional magnetic fluids cannot transmit light, and magnetic ionic liquids such as 1-butyl-3-methylimidazolium tetrachloroferrate are colored dark brown. A colorless and transparent magnetic fluid, magnetic ionic liquid, is an interesting magnetic material both visually and photochemically, but has not yet been obtained. There is a need for a colorless and transparent magnetic fluid and magnetic ionic liquid that are excellent in visibility and visible light transmission.
そこで、発明者らは鋭意研究を重ねた結果、本発明を完成するに至った。 As a result of intensive studies, the inventors have completed the present invention.
本発明は、有機オニウムカチオンとテトラハロゲノジスプロサートアニオンからなるジスプロシウム誘導体に関するもので、有機カチオンが下記一般式 The present invention relates to a dysprosium derivative comprising an organic onium cation and a tetrahalogenodisprosate anion, wherein the organic cation is represented by the following general formula:
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７はそれぞれ独立に水素、アルキル基、アルキルオキシメチル基、アルケニル基、芳香環、複素環から選択される）で示される有機カチオンから選択される一つとアニオンがテトラハロゲノジスプロサートから成るジスプロシウム誘導体である。Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently selected from hydrogen, alkyl group, alkyloxymethyl group, alkenyl group, aromatic ring, and heterocyclic ring And an anion selected from organic cations represented by) is a dysprosium derivative comprising tetrahalogenodisprosate.
以下に本発明の代表例として、下記構造式で示される１−ブチル−３−メチルイミダゾリウムテトラクロロジスプロサートを取り上げ、本発明の有用性を明らかにする。 Hereinafter, as a representative example of the present invention, 1-butyl-3-methylimidazolium tetrachlorodisprosate represented by the following structural formula will be taken up to clarify the usefulness of the present invention.
１−ブチル−３−メチルイミダゾリウムテトラクロロジスプロサートは下記反応式に従って合成することができる。 1-butyl-3-methylimidazolium tetrachlorodisprosate can be synthesized according to the following reaction formula.
等モルの１−ブチル−３−メチルイミダゾリウムクロリド及び三塩化ジスプロシウムを混合し、加熱する。反応温度は５０℃から１５０℃の間で適宜選択されるが、好ましくは９０℃付近である。反応時間は３０分から２４時間の間で適宜選択される。反応溶媒は特に用いなくても良いが、酢酸エチル、アセトニトリル等の有機溶媒を用いても良い。反応終了後、室温まで冷却することにより、白色固体が得られる。得られた１−ブチル−３−メチルイミダゾリウムテトラクロロジスプロサートはごく少量の水を添加することにより、均一な透明液体となる。この液体は磁性を有しており、磁石を近づけると前述の１−ブチル−３−メチルイミダゾリウムテトラクロロフェラートと同様に磁石に引き寄せられる。 Equimolar amounts of 1-butyl-3-methylimidazolium chloride and dysprosium trichloride are mixed and heated. The reaction temperature is appropriately selected between 50 ° C. and 150 ° C., preferably about 90 ° C. The reaction time is appropriately selected between 30 minutes and 24 hours. A reaction solvent is not particularly required, but an organic solvent such as ethyl acetate or acetonitrile may be used. After completion of the reaction, a white solid is obtained by cooling to room temperature. The obtained 1-butyl-3-methylimidazolium tetrachlorodisprosate becomes a uniform transparent liquid by adding a very small amount of water. This liquid has magnetism, and when the magnet is brought close to it, it is attracted to the magnet in the same manner as 1-butyl-3-methylimidazolium tetrachloroferrate.
上記のように、本発明に係るジスプロシウム誘導体は極めて容易に合成することができ上記のように、本発明に係るジスプロシウム誘導体は極めて容易に合成することができる。１−ブチル−３−メチルイミダゾリウムテトラクロロジスプロサートは少量の水を添加することにより均一な無色透明の液体となる。この液体は磁性を有しており、磁石を近づけると前述の１−ブチル−３−メチルイミダゾリウムテトラクロロフェラートと同様に磁石に引き寄せられる。また、適当な色素を溶解させ着色することにより、光透過性を任意にコントロールできる。以上のように、本発明に係るジスプロシウム誘導体は極めて有用な視覚性、可視光の透過性に優れた無色透明の新規磁性流体、磁性イオン液体であると言える。 As described above, the dysprosium derivative according to the present invention can be synthesized very easily, and as described above, the dysprosium derivative according to the present invention can be synthesized very easily. 1-butyl-3-methylimidazolium tetrachlorodisprosate becomes a uniform colorless and transparent liquid by adding a small amount of water. This liquid has magnetism, and when the magnet is brought close to it, it is attracted to the magnet in the same manner as 1-butyl-3-methylimidazolium tetrachloroferrate. Moreover, light transmittance can be arbitrarily controlled by dissolving and coloring an appropriate pigment. As described above, it can be said that the dysprosium derivative according to the present invention is a novel colorless and transparent magnetic fluid and magnetic ionic liquid that are extremely useful for visual and visible light transmission.
以下、本発明を実施例により更に詳細に説明する。なお、本発明の範囲は、かかる実施例に限定されないことは言うまでもない。本発明の範囲内では変形が可能なことは当業者には明らかであろう。 Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the scope of the present invention is not limited to such examples. It will be apparent to those skilled in the art that variations are possible within the scope of the invention.
実施例
１−ブチル−３−メチルイミダゾリウムテトラクロロジスプロサートの合成
乾燥窒素置換したグローブボックス中、１−ブチル−３−メチルイミダゾリウムクロリド０．７４９ｇ（４．２９ｍｍｏｌ）と塩化ジスプロシウム六水和物１．６２ｇ（４．２９ｍｍｏｌ）を反応容器に入れ、乾燥雰囲気下、約１３０℃に加熱することにより融解させた。次いで反応混合物の水分を蒸発させることにより１−ブチル−３−メチルイミダゾリウムテトラクロロジスプロサートをほぼ定量的に得た。以下に主な物性を示す。
融点：＞１５０℃
１Ｈ−ＮＭＲ（ＣＤ３ＣＮ）：δ８．８９（１Ｈ，Ｓ），７．２２（２Ｈ，ｄ），４．３（３Ｈ，ｓ），４．１（２Ｈ，ｔ），２．２（２Ｈ，ｍ），１．２（２Ｈ，ｍ），０．９（３Ｈ，ｔ）；ＵＶ−ＶＩＳ：４００−１２００ｎｍ領域には特に大きな吸収はない。ラマンスペクトルには原料であるＤｙＣｌ３６Ｈ２Ｏ由来のバンド（１５３．６，２０５．３ｃｍ−１）はない。 Example
Synthesis of 1-butyl-3-methylimidazolium tetrachlorodisprosate In a dry nitrogen-substituted glove box, 0.749 g (4.29 mmol) of 1-butyl-3-methylimidazolium chloride and dysprosium chloride hexahydrate 1 .62 g (4.29 mmol) was placed in a reaction vessel and melted by heating to about 130 ° C. in a dry atmosphere. Then, 1-butyl-3-methylimidazolium tetrachlorodisprosate was obtained almost quantitatively by evaporating the water in the reaction mixture. The main physical properties are shown below.
Melting point:> 150 ° C
1 H-NMR (CD 3 CN): δ 8.89 (1H, S), 7.22 (2H, d), 4.3 (3H, s), 4.1 (2H, t), 2.2 ( 2H, m), 1.2 (2H, m), 0.9 (3H, t); UV-VIS: There is no particularly large absorption in the 400-1200 nm region. There is no band (153.6, 205.3 cm −1 ) derived from the raw material DyCl 3 6H 2 O in the Raman spectrum.
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| JP2005354084A JP2007131608A (en) | 2005-11-10 | 2005-11-10 | New dysprosium derivative |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011506088A (en) * | 2007-12-20 | 2011-03-03 | プロイオニック プロダクション オブ イオニック サブスタンシス ゲーエムベーハー ウント コムパニー カーゲー | Use of magnetic and ionic liquids as extractants |
| CN102010435A (en) * | 2010-10-22 | 2011-04-13 | 太原理工大学 | Preparation method of dysprosium coordinated compound emitting pale yellow light |
| JP2012191150A (en) * | 2011-03-09 | 2012-10-04 | Hiroshi Kashihara | Ferromagnetic organic magnetic fluid |
| CN102942527A (en) * | 2012-10-17 | 2013-02-27 | 西北工业大学 | Vinyl alkyl imidazole tetrathiocyanate cobalt (II) magnetic ionic liquids and synthetic methods thereof |
| CN103073500A (en) * | 2013-01-06 | 2013-05-01 | 四川大学 | Rare earth metal ionic liquid, preparation method and application thereof |
| JP2013199462A (en) * | 2012-03-26 | 2013-10-03 | Hiroshi Kashihara | Method for synthesizing novel ferromagnetic organic magnetic fluid and method for using the same |
| JP2015111690A (en) * | 2014-12-10 | 2015-06-18 | 樫原 宏 | Polyhydric alcohol type and catechol borate type ferromagnetic organic magnetic fluid |
| JP2015111676A (en) * | 2014-11-23 | 2015-06-18 | 樫原 宏 | Ether chelate and polyether chelate ferromagnetic organic magnetic fluid |
| JP2015127391A (en) * | 2014-09-24 | 2015-07-09 | 樫原 宏 | Method of synthesizing and using novel ferromagnetic organic magnetic fluid |
| WO2019131089A1 (en) | 2017-12-26 | 2019-07-04 | 矢崎エナジーシステム株式会社 | Rotary fitting |
| WO2019131085A1 (en) | 2017-12-26 | 2019-07-04 | 矢崎エナジーシステム株式会社 | Structure and composite structure |
| WO2019131091A1 (en) | 2017-12-26 | 2019-07-04 | 矢崎エナジーシステム株式会社 | Latent heat storage building element |
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-
2005
- 2005-11-10 JP JP2005354084A patent/JP2007131608A/en not_active Withdrawn
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011506088A (en) * | 2007-12-20 | 2011-03-03 | プロイオニック プロダクション オブ イオニック サブスタンシス ゲーエムベーハー ウント コムパニー カーゲー | Use of magnetic and ionic liquids as extractants |
| CN102010435A (en) * | 2010-10-22 | 2011-04-13 | 太原理工大学 | Preparation method of dysprosium coordinated compound emitting pale yellow light |
| JP2012191150A (en) * | 2011-03-09 | 2012-10-04 | Hiroshi Kashihara | Ferromagnetic organic magnetic fluid |
| JP2013199462A (en) * | 2012-03-26 | 2013-10-03 | Hiroshi Kashihara | Method for synthesizing novel ferromagnetic organic magnetic fluid and method for using the same |
| CN102942527A (en) * | 2012-10-17 | 2013-02-27 | 西北工业大学 | Vinyl alkyl imidazole tetrathiocyanate cobalt (II) magnetic ionic liquids and synthetic methods thereof |
| CN103073500A (en) * | 2013-01-06 | 2013-05-01 | 四川大学 | Rare earth metal ionic liquid, preparation method and application thereof |
| JP2015127391A (en) * | 2014-09-24 | 2015-07-09 | 樫原 宏 | Method of synthesizing and using novel ferromagnetic organic magnetic fluid |
| JP2015111676A (en) * | 2014-11-23 | 2015-06-18 | 樫原 宏 | Ether chelate and polyether chelate ferromagnetic organic magnetic fluid |
| JP2015111690A (en) * | 2014-12-10 | 2015-06-18 | 樫原 宏 | Polyhydric alcohol type and catechol borate type ferromagnetic organic magnetic fluid |
| WO2019131089A1 (en) | 2017-12-26 | 2019-07-04 | 矢崎エナジーシステム株式会社 | Rotary fitting |
| WO2019131085A1 (en) | 2017-12-26 | 2019-07-04 | 矢崎エナジーシステム株式会社 | Structure and composite structure |
| WO2019131091A1 (en) | 2017-12-26 | 2019-07-04 | 矢崎エナジーシステム株式会社 | Latent heat storage building element |
| US11306977B2 (en) | 2017-12-26 | 2022-04-19 | Yazaki Energy System Corporation | Rotary fitting |
| DE112018007087B4 (en) | 2018-02-16 | 2023-02-02 | Yazaki Energy System Corporation | Latent heat storage body |
| US11643585B2 (en) | 2018-02-16 | 2023-05-09 | Yazaki Energy System Corporation | Latent heat storage body |
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