JP2007332098A - Method for producing ruthenium-organic complex - Google Patents
Method for producing ruthenium-organic complex Download PDFInfo
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- JP2007332098A JP2007332098A JP2006167708A JP2006167708A JP2007332098A JP 2007332098 A JP2007332098 A JP 2007332098A JP 2006167708 A JP2006167708 A JP 2006167708A JP 2006167708 A JP2006167708 A JP 2006167708A JP 2007332098 A JP2007332098 A JP 2007332098A
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- butyl
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 5
- RSHBFZCIFFBTEW-UHFFFAOYSA-M tetrabutylazanium;thiocyanate Chemical compound [S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC RSHBFZCIFFBTEW-UHFFFAOYSA-M 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims 1
- 239000011343 solid material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000012153 distilled water Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000013076 target substance Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-DYCDLGHISA-M Sodium hydroxide-d Chemical compound [Na+].[2H][O-] HEMHJVSKTPXQMS-DYCDLGHISA-M 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012327 Ruthenium complex Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- -1 tetra (n-butyl) ammonium cations Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FRYSEKUUHUUJPX-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=CC=2)=C1 FRYSEKUUHUUJPX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HXNXAEYAXNPLHJ-UHFFFAOYSA-N butyl thiocyanate Chemical compound CCCCSC#N HXNXAEYAXNPLHJ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- FHNRXCZVLIJCGL-UHFFFAOYSA-N ruthenium(2+) tetrabutylazanium Chemical compound [Ru+2].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC FHNRXCZVLIJCGL-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
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Abstract
Description
本発明は、多孔性半導体層に用いる増感色素に好適なルテニウム有機錯体の製造方法に関する。
より詳しくは、太陽電池等の多孔性半導体層に用いる増感色素に好適なルテニウム有機錯体であるシス−ビス（２，２'−ビピリジン−４−カルボン酸−４'−カルボキシラート−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）酸ビス［テトラ(ｎ−ブチル)アンモニウム］（以下、「ＴＢＡ錯体」と略称することもある）を製造する方法に関する。
The present invention relates to a method for producing a ruthenium organic complex suitable for a sensitizing dye used for a porous semiconductor layer.
More specifically, cis-bis (2,2′-bipyridine-4-carboxylic acid-4′-carboxylate-N, N), which is a ruthenium organic complex suitable for a sensitizing dye used in a porous semiconductor layer such as a solar cell. ′) A method for producing bis [thiocyanato-N) ruthenium (II) bis [tetra (n-butyl) ammonium] (hereinafter sometimes abbreviated as “TBA complex”).
［先行技術文献］
ルテニウム有機錯体であるビピリジンジカルボン酸−ルテニウム錯体は、光増感作用を有する増感色素として有用な物質であることが知られており、このような光増感作用を有するビピリジンジカルボン酸−ルテニウム錯体は、例えば、太陽電池などの光電変換材料に使用されている。
そのビピリジンジカルボン酸−ルテニウム錯体の製造方法は、例えば非特許文献１及び２に記載されており、両文献にはシス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）を製造することが記載されている。
Bipyridine dicarboxylic acid-ruthenium complex, which is a ruthenium organic complex, is known to be a useful substance as a sensitizing dye having a photosensitizing action, and a bipyridine dicarboxylic acid-ruthenium complex having such a photosensitizing action. Is used for photoelectric conversion materials such as solar cells.
The production method of the bipyridinedicarboxylic acid-ruthenium complex is described, for example, in
その太陽電池の光電変換材料用としてのビピリジンジカルボン酸−ルテニウム錯体としてはＴＢＡ錯体も既知（非特許文献３及び特許文献４参照、これらにはＴＢＡ錯体が、ビス（テトラブチルアンモニウム）シス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）という名称で記載されている）であり、それは前記両非特許文献に記載のシス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）に比し、太陽電池の特性を示す光電変化効率が優れていることもわかっている（特許文献４参照）。
A TBA complex is also known as a bipyridinedicarboxylic acid-ruthenium complex for a photoelectric conversion material of the solar cell (see Non-Patent
その優れた特性を持つＴＢＡ錯体の製造方法は非特許文献３に提案されている。
その提案の方法では、本発明の製造方法と同様にシス−ジクロロ−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ルテニウム(II)［以下、「シス−ジクロロ錯体」と略称することもある］を出発原料物質とし、それにチオシアン酸ナトリウムを反応させて、まずシス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）を製造する。
A method for producing a TBA complex having such excellent characteristics is proposed in
In the proposed method, cis-dichloro-bis (2,2′-bipyridine-4,4′-dicarboxylic acid-N, N ′) ruthenium (II) [hereinafter referred to as “cis- Dichloro complex ”may be abbreviated as“ starting material ”, and sodium thiocyanate is reacted therewith, first, cis-bis (2,2′-bipyridine-4,4′-dicarboxylic acid-N, N ′) Bis (thiocyanato-N) ruthenium (II) is produced.
次いで、製造されたシス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）に、水酸化テトラ（ｎ−ブチル）アンモニウム（以下、「ＴＢＡＯＨ」と略称することもある）を反応させ、シス−ジチオシアナト−Ｎ−ビス（２，２'−ビピリジル−４，４'−ジカルボキシラート−Ｎ，Ｎ’）ルテニウム(II)酸テトラキス[テトラ(ｎ−ブチル)アンモニウム]を製造する。
その後、この製造されたシス−ジチオシアナト−Ｎ−ビス（２，２'−ビピリジン−４，４'−ジカルボキシラート−Ｎ，Ｎ’）ルテニウム(II) 酸テトラキス[テトラ(ｎ−ブチル)アンモニウム]に希薄硝酸を滴下することにより、本発明の製造目的物質に該当するＴＢＡ錯体が製造される。
Next, the cis-bis (2,2′-bipyridine-4,4′-dicarboxylic acid-N, N ′) bis (thiocyanato-N) ruthenium (II) produced was added to tetra (n-butyl) ammonium hydroxide. (Hereinafter also abbreviated as “TBAOH”), and cis-dithiocyanato-N-bis (2,2′-bipyridyl-4,4′-dicarboxylate-N, N ′) ruthenium (II) The acid tetrakis [tetra (n-butyl) ammonium] is prepared.
This prepared cis-dithiocyanato-N-bis (2,2′-bipyridine-4,4′-dicarboxylate-N, N ′) ruthenium (II) acid tetrakis [tetra (n-butyl) ammonium] By diluting dilute nitric acid, a TBA complex corresponding to the production target substance of the present invention is produced.
本発明が製造目的物とするＴＢＡ錯体は、前記したとおり太陽電池の光電変換材料用として用いた場合には、優れた光電変化効率を発現することができるものである。
しかしながら、その従来における製造方法はシス−ジクロロ錯体を出発原料とした場合には前記非特許文献３に記載されているとおり３段階の工程を必要とするものであった。
As described above, the TBA complex to be produced by the present invention can exhibit excellent photoelectric conversion efficiency when used as a photoelectric conversion material for solar cells.
However, the conventional production method requires three steps as described in Non-Patent
すなわち、シス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビ
ス（チオシアナト−Ｎ）ルテニウム（II）を製造する工程、シス−ビス（２，２'−ビピス（チオシアナト−Ｎ）ルテニウム（II）を製造する工程、シス−ビス（２，２'−ビピリジル−４，４'−ジカルボキシラート−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム(II)酸テトラキス[テトラ（ｎ−ブチル）アンモニウム]を製造する工程及びＴＢＡ錯体を製造する工程の３工程を経由することにより、換言すれば２つの中間体を経由して、本発明の製造目的物質は製造されることになる。
That is, a step of producing cis-bis (2,2′-bipyridine-4,4′-dicarboxylic acid-N, N ′) bis (thiocyanato-N) ruthenium (II), cis-bis (2,2′- A step of producing bipis (thiocyanato-N) ruthenium (II), cis-bis (2,2′-bipyridyl-4,4′-dicarboxylate-N, N ′) bis (thiocyanato-N) ruthenium (II) The production target substance of the present invention is obtained by going through three steps of producing a tetrakis [tetra (n-butyl) ammonium acid] and a step of producing a TBA complex, in other words, via two intermediates. Will be manufactured.
そこで、本発明者は、この製造方法をより簡略化すべく前記従来技術の製造プロセスを検討した。
その際に、４つある全てのカルボキシル基が電離した陰イオンとなり、それに４っのテトラ（ｎ−ブチル）アンモニウム陽イオンがついた塩ができ、その後希薄の硝酸の処理により２つのカルボキシル基からテトラ（ｎ−ブチル）アンモニウムイオンが分離することにより本発明の製造目的物質が得られていることに着目して、鋭意研究を重ね、その結果本発明を開発することに成功した。
また、得られた目的物質は高純度のものであった。
Therefore, the present inventor examined the manufacturing process of the prior art in order to further simplify the manufacturing method.
At that time, all four carboxyl groups become ionized anions, and then a salt with four tetra (n-butyl) ammonium cations is formed, which is then treated with dilute nitric acid from the two carboxyl groups. Focusing on the fact that the production target substance of the present invention was obtained by separation of tetra (n-butyl) ammonium ions, earnest research was repeated, and as a result, the present invention was successfully developed.
The obtained target substance was of high purity.
したがって、本発明は、太陽電池の光電変換材料用として用いた場合には、優れた光電変化効率を発現することができるＴＢＡ錯体を簡便で、効率的に製造する
ことができる、すなわち２つの中間体を経由することなく目的製造物質を製造することができる新規な方法を提供することを解決すべき課題、すなわち目的とするものである。
また、本発明は前記した物質を高純度で製造することも目的とするものである。
Therefore, the present invention can easily and efficiently produce a TBA complex that can exhibit excellent photoelectric conversion efficiency when used as a photoelectric conversion material for a solar cell. It is a problem to be solved, ie, an object, to provide a novel method capable of producing a target production substance without going through the body.
Another object of the present invention is to produce the aforementioned substance with high purity.
本発明者らは、前記したとおり鋭意研究を重ねＴＢＡ錯体の新たな製造方法の開発に成功したものであり、それはシス−ジクロロ錯体に、ＴＢＡＯＨを反応させ、次いでチオシアン酸テトラ（ｎ−ブチル）アンモニウム（以下、「ＴＢＡＳＣＮ」と略称することもある）と反応させることを特徴とするものである。 As described above, the present inventors have conducted extensive research and succeeded in developing a new method for producing a TBA complex, which is obtained by reacting a cis-dichloro complex with TBAOH and then tetra (n-butyl) thiocyanate. It is characterized by reacting with ammonium (hereinafter sometimes abbreviated as “TBASCN”).
また、その製造方法においては、ＴＢＡＳＣＮはシス−ジクロロ錯体の１モルに対し２〜５モルを用いることが特に好ましい。
さらに、ＴＢＡＳＣＮとの反応をマイクロ波照射下で行うのが好ましく、更にその反応後減圧濃縮し、得られた固体物質を水に溶解又は懸濁させて、その水溶液又は懸濁液を希硝酸水溶液でｐＨ３．０〜４．１に調整し、調整後固液分離し、分離後精製するのが好ましい。
Moreover, in the manufacturing method, it is especially preferable to use 2-5 mol of TBASCN per 1 mol of the cis-dichloro complex.
Further, the reaction with TBASCN is preferably carried out under microwave irradiation, and further concentrated under reduced pressure after the reaction. The obtained solid substance is dissolved or suspended in water, and the aqueous solution or suspension is diluted with dilute nitric acid aqueous solution. It is preferable to adjust the pH to 3.0 to 4.1, solid-liquid separation after adjustment, and purification after separation.
本発明では、太陽電池の光電変換材料用として好適に用いることができる、光電変化効
率に優れたＴＢＡ錯体を、従来方法のように３段階の工程を用いることなく、すなわち２つの中間体を経ることなく、簡便で、かつ効率的に製造する製造方法を提供することができる。
さらに、本発明の製造方法では、目的製造物質を高純度で得ることができる。
In the present invention, a TBA complex excellent in photoelectric conversion efficiency, which can be suitably used for a photoelectric conversion material of a solar cell, passes through two intermediates without using three steps as in the conventional method. Therefore, it is possible to provide a manufacturing method that is simple and efficient.
Furthermore, in the production method of the present invention, the target production substance can be obtained with high purity.
本発明においては、ＴＢＡＯＨは、シス−ジクロロ錯体に対して、従来の方法のように過剰に用いるのではなく、目的製造物質に必要な当量程度、すなわち２モル前後用いており、これにより従来方法のようにシス−ビス（２，２'−ビピリジル−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム(II)を一旦生成することもなく、直接目的製造物質を製造することができるものである。
In the present invention, TBAOH is not used excessively as in the conventional method with respect to the cis-dichloro complex, but is used in an equivalent amount necessary for the target production substance, that is, around 2 mol. As described above, cis-bis (2,2′-bipyridyl-4,4′-dicarboxylic acid-N, N ′) bis (thiocyanato-N) ruthenium (II) is not generated once, It can be manufactured.
以下において、本発明について、発明を実施するための最良の形態を含む発明の実施の形態に関し詳述するが、本発明は、この実施の形態によって何等限定されるものではなく、特許請求の範囲によって特定されるものであることはいうまでもない。 Hereinafter, the present invention will be described in detail with respect to an embodiment of the invention including the best mode for carrying out the invention, but the present invention is not limited in any way by this embodiment, and claims Needless to say, it is specified by.
本発明の製造方法における出発原料であるシス−ジクロロ錯体は前記したとおり既知物質であり、その製造方法は、前記特許文献１、２及び３、並びに非特許文献３に記載されており、それらを特に制限されることなく適宜採用し製造すればよい。
また、そのシス−ジクロロ錯体は市販もされており、それを利用してもよい。
The cis-dichloro complex, which is a starting material in the production method of the present invention, is a known substance as described above, and its production method is described in
The cis-dichloro complex is also commercially available and may be used.
本発明では、このシス−ジクロロ錯体とＴＢＡＯＨとをまず混合し反応させる。
その際には、シス−ジクロロ錯体を、Ｎ，Ｎ−ジメチルホルムアミド（以下、「ＤＭＦ」と略称する）等の有機溶媒を水に溶かした溶媒水溶液に溶解し、これにＴＢＡＯＨの水溶液を添加し混合する。
In the present invention, the cis-dichloro complex and TBAOH are first mixed and reacted.
In this case, the cis-dichloro complex is dissolved in an aqueous solvent obtained by dissolving an organic solvent such as N, N-dimethylformamide (hereinafter abbreviated as “DMF”) in water, and an aqueous solution of TBAOH is added thereto. Mix.
その際には、添加後超音波を作用させ、その後攪拌するのがよいが、これらは本発明においては必要不可欠するものではない。
その際に用いる前記溶媒水溶液における溶媒としては、水に溶解し、溶解後の溶媒水溶液がシス−ジクロロ錯体を溶解することができるものであれば特に制限されることなく使用可能であり、それには前記ＤＭＦ以外に、ジメチルスルホキシド（以下、「ＤＭＳＯ」と略称する）、エチレングリコール等が例示できる。
これらの中でも沸点が８０〜２００℃の範囲である溶媒が好ましく用いられ、ＤＭＦがより好ましく用いられる。
In that case, it is preferable to apply ultrasonic waves after the addition and then stir, but these are not essential in the present invention.
As the solvent in the solvent aqueous solution used at that time, it can be used without particular limitation as long as it dissolves in water and the dissolved solvent aqueous solution can dissolve the cis-dichloro complex. In addition to the DMF, dimethyl sulfoxide (hereinafter abbreviated as “DMSO”), ethylene glycol and the like can be exemplified.
Among these, a solvent having a boiling point in the range of 80 to 200 ° C. is preferably used, and DMF is more preferably used.
また、有機溶媒を水に溶かした溶媒水溶液における有機溶媒と水との比率は、使用した有機溶媒によるが、９：１〜１：９がよい。
その際にはＴＢＡＯＨは１０％水溶液を用いるのがよく、それを用いてＴＢＡＯＨのモル濃度が必要量になるように溶液を調製する（すなわち、必要な当量濃度、具体的には２モル前後）。
Moreover, although the ratio of the organic solvent and water in the solvent aqueous solution which melt | dissolved the organic solvent in water depends on the used organic solvent, 9: 1 to 1: 9 are good.
In that case, it is preferable to use a 10% aqueous solution of TBAOH, and a solution is prepared by using it so that the molar concentration of TBAOH becomes a necessary amount (that is, the required equivalent concentration, specifically around 2 mol). .
次いで、シス−ジクロロ錯体とＴＢＡＯＨとを混合し反応させた溶液にＴＢＡＳＣＮを添加し、反応させる。
その際には、ＴＢＡＯＨはシス−ジクロロ錯体に対して、目的製造物質に必要な当量程度、すなわち２モル前後用いるのがよい。
Subsequently, TBASCN is added to the solution obtained by mixing and reacting the cis-dichloro complex and TBAOH, and reacted.
In this case, TBAOH is preferably used in an equivalent amount necessary for the target production substance, that is, about 2 mol, relative to the cis-dichloro complex.
具体的には、シス−ジクロロ錯体の１モルに対しＴＢＡＯＨの１．８〜２．２モルを用いるのが好ましく、これにより従来方法のようにシス−ビス（２，２'−ビピリジン−４，４'−ジカルボン酸−Ｎ，Ｎ’）ビス（チオシアナト−Ｎ）ルテニウム（II）を一旦生成することもなく、直接目的製造物質を製造する。 Specifically, it is preferable to use 1.8 to 2.2 mol of TBAOH with respect to 1 mol of the cis-dichloro complex, whereby cis-bis (2,2′-bipyridine-4, 4′-dicarboxylic acid-N, N ′) bis (thiocyanato-N) ruthenium (II) is directly produced without producing the target product directly.
また、前記したところにおいては、ＴＢＡＳＣＮの混合は、シス−ジクロロ錯体とＴＢＡＯＨとの混合後に行っており、それが好ましいが、その３者の混合は同時に行ってもよく、その場合にも目的製造物質を得ることは可能であり、本発明はそのような態様をも包含するものである。
さらに、シス−ジクロロ錯体とＴＢＡＯＨとの中間生成物を単離する必要もなく、簡便なものとなっている。
Moreover, in the above-mentioned place, mixing of TBASCN is performed after mixing of cis-dichloro complex and TBAOH, and it is preferable, but mixing of the three may be performed at the same time. It is possible to obtain a substance, and the present invention includes such an embodiment.
Furthermore, there is no need to isolate an intermediate product between the cis-dichloro complex and TBAOH, which is simple.
ＴＢＡＯＨ及びＴＢＡＳＣＮとの反応条件は、例えば、ＤＭＦ溶液を用いた場合においては、温度は８０℃以上１５３℃以下、圧力は５ｂａｒ以下、ｐＨ５以下の条件で行うのが好ましい。
そのＴＢＡＳＣＮとの混合時にも、特に限定されるわけではないが超音波を作用させるのがよい。
さらに、前記反応は、特に限定されるわけではないがヘリウムガス、窒素ガス及びアルゴンガス等の不活性ガス雰囲気中、でマイクロ波照射下で行うのが好ましい。
For example, when a DMF solution is used, the reaction conditions with TBAOH and TBASCN are preferably performed under conditions of a temperature of 80 ° C. or more and 153 ° C. or less, a pressure of 5 bar or less, and a pH of 5 or less.
While mixing with TBASCN, although not particularly limited, it is preferable to apply ultrasonic waves.
Further, the reaction is not particularly limited, but is preferably performed under microwave irradiation in an inert gas atmosphere such as helium gas, nitrogen gas, and argon gas.
その際のマイクロ波出力装置としては、市販のものが使用でき、その際に用いられるマイクロ波の波長は、通常２．４〜２．５ＧＨｚ、好ましくは２．４５ＧＨｚ（±３０ＭＨｚ）である。
マイクロ波の出力は、反応液の量に応じて適宜選択されるが、通常３０Ｗ〜１５００Ｗ、好ましくは１００〜８００Ｗの範囲である。
As the microwave output device at that time, a commercially available device can be used, and the wavelength of the microwave used at that time is usually 2.4 to 2.5 GHz, preferably 2.45 GHz (± 30 MHz).
Although the output of a microwave is suitably selected according to the quantity of reaction liquid, it is 30W-1500W normally, Preferably it is the range of 100-800W.
その後、減圧下で溶媒を除去し、乾固させ、残った固体を水に溶解させ、得られた水溶液に希硝酸を添加し、ｐＨを３．０〜４．１に調整するのがよく、好ましくは３．４〜３．９に調整するのがよい。
このｐＨ調整後、水溶液中に存在する固体を吸引濾過等の固液分離により分離し、アセトン等の溶媒で洗浄し、乾燥して製造目的物質を得る。
その固液分離は、濾過に限らず固体と液体を分離することができるものであれば特に制限されることなく各種手段が採用することが可能であり、それには遠心分離、デカンテーションあるいは再結晶法等が例示できる。
Thereafter, the solvent is removed under reduced pressure, dried, the remaining solid is dissolved in water, dilute nitric acid is added to the resulting aqueous solution, and the pH is adjusted to 3.0 to 4.1. It is preferable to adjust to 3.4 to 3.9.
After this pH adjustment, the solid present in the aqueous solution is separated by solid-liquid separation such as suction filtration, washed with a solvent such as acetone, and dried to obtain the production target substance.
The solid-liquid separation is not limited to filtration, and any means can be adopted without particular limitation as long as it can separate solids and liquids. Centrifugation, decantation, or recrystallization can be used. For example, law
洗浄用の溶媒にも、目的製造物質を溶解することなく洗浄することができるものであれば、アセトン以外の各種のものが特に制限されることなく利用可能であり、それにはジクロロメタンあるいはクロロホルム等が例示できる。
乾燥にも、目的製造物質を乾燥することができるものであれば、各種のものが特に制限されることなく利用可能であり、それには真空乾燥、真空加熱乾燥、真空凍結乾燥及び加熱乾燥等が例示できる。
As the washing solvent, various substances other than acetone can be used without particular limitation as long as they can be washed without dissolving the target production substance, such as dichloromethane or chloroform. It can be illustrated.
As long as the target production substance can be dried, various types of substances can be used without particular limitation, and examples thereof include vacuum drying, vacuum heat drying, vacuum freeze drying, and heat drying. It can be illustrated.
以下に、本発明の実施例を示すが、本発明は、本実施例によってなんら限定されるものではなく、特許請求の範囲の規定によって特定されるものであることはいうまでもない。
シス−ジクロロ錯体０．５ｇをＤＭＦ５０％水溶液（ＤＭＦと純水を体積比で１：１で混合した溶媒）１００ｍＬに溶解し、これにＴＢＡＯＨ（１０％水溶液）３．２ｍＬ（シス−ジクロロ錯体１モルに対し、ＴＢＡＯＨを２モル）添加し、この混合溶液に超音波を１０分間作用させ、その作用後３０分間攪拌した。
Examples of the present invention will be described below, but the present invention is not limited to the examples at all, and it goes without saying that the invention is specified by the definition of the scope of claims.
0.5 g of cis-dichloro complex was dissolved in 100 mL of DMF 50% aqueous solution (solvent in which DMF and pure water were mixed at a volume ratio of 1: 1), and 3.2 mL of TBAOH (10% aqueous solution) was added thereto (cis-dichloro complex 1). 2 mol of TBAOH was added to the mole), and ultrasonic waves were allowed to act on the mixed solution for 10 minutes, followed by stirring for 30 minutes.
その攪拌後、この溶液にＴＢＡＳＣＮ ０．８６ｇを加え、同出力の超音波を１０分間作用させ、その後アルゴンガスを溶液中に１０分間通して脱気し、アルゴン雰囲気下で、マイクロ波（波長２．４５ＧＨｚ、出力５４０Ｗ）を２０分間照射した。
その照射後、照射された液を濾過器で濾過し、濾液を減圧下で除去し乾固させた。
その乾固後、残った固体を約１５℃の純水６０ｍＬに溶解し、得られた水溶液に希硝酸（０．５Ｎ）を２時間かけて滴下し、ｐＨ３．９以下に調整した。
After the stirring, 0.86 g of TBASCN was added to this solution, and the same output ultrasonic wave was allowed to act for 10 minutes, and then argon gas was passed through the solution for 10 minutes to deaerate it. .45 GHz, output 540 W) was irradiated for 20 minutes.
After the irradiation, the irradiated liquid was filtered with a filter, and the filtrate was removed under reduced pressure to dryness.
After the solidification, the remaining solid was dissolved in 60 mL of pure water at about 15 ° C., and diluted nitric acid (0.5 N) was added dropwise to the obtained aqueous solution over 2 hours to adjust the pH to 3.9 or lower.
このｐＨ調整により析出させた固体を濾過器を用いて吸引濾過し、分離した固体を８時間真空乾燥した。
その後乾燥物をアセトン３０ｍＬ、ジエチルエーテル１０ｍＬにて洗浄し、大気中にて７５℃で８時間乾燥した。
得られたＴＢＡ錯体を1Ｈ ＮＭＲ（Ｄ2Ｏ／ＮａＯＤ）で分析したところ、図１に示すように不純物を示すシグナルは検出されなかった。
なお、その際の収量は０．７１９ｇ、収率は８２％であった。
The solid precipitated by this pH adjustment was subjected to suction filtration using a filter, and the separated solid was vacuum-dried for 8 hours.
Thereafter, the dried product was washed with 30 mL of acetone and 10 mL of diethyl ether, and dried in the air at 75 ° C. for 8 hours.
When the obtained TBA complex was analyzed by 1 H NMR (D 2 O / NaOD), no signal indicating an impurity was detected as shown in FIG.
The yield at that time was 0.719 g, and the yield was 82%.
そして、1Ｈ ＮＭＲの結果について更に解析し、以下のとおり目的の物質であることを確認した。
すなわち、ｄｃｂｐｙ配位子の存在及びＴＢＡ+の存在は以下のとおり確認した。
That is, the presence of the dcbpy ligand and the presence of TBA + were confirmed as follows.
また、組成及び純度については、1Ｈ ＮＭＲ（Ｄ2Ｏ／ＮａＯＤ）の分析結果から以下のとおりと判断した。
［組成について］
それぞれのプロトンをシグナル強度比でみて決定した。
例えば、ＴＢＡ+のメチレン鎖（−ＣＨ2−）とｄｃｂｐｙの６位とのプロトン比は８：１となることから、錯体陰イオン１つに対して２つのＴＢＡ+が塩を形成したものと推測される。してみると、錯体は−２価陰イオンである。
［純度について］
図１に示すスペクトルのように、不純物を示すシグナルは検出されなかった。
The composition and purity were determined as follows from the analysis results of 1 H NMR (D 2 O / NaOD).
[Composition]
Each proton was determined by the signal intensity ratio.
For example, since the proton ratio between the methylene chain of TBA + (—CH 2 —) and the 6-position of dcbpy is 8: 1, two TBA + form a salt with respect to one complex anion. Guessed. As a result, the complex is a -2 anion.
[Purity]
As in the spectrum shown in FIG. 1, no signal indicating an impurity was detected.
シス−ジクロロ錯体０．５ｇ、ＴＢＡＯＨ（１０％水溶液）３．２ｍｌ（シス−ジクロロ錯体１モルに対し、ＴＢＡＯＨを２モル）、ＴＢＡＳＣＮ ０．８６gを同時に反応容器に入れ、更にＮ，Ｎ−ジメチルホルムアミド水溶液１００ｍｌを加え、この混合溶液に超
音波を１０分間作用させ、その作用後３０分間攪拌した。
その攪拌後、アルゴンガスを溶液中に１０分間通して脱気し、アルゴン雰囲気下で、マイクロ波（波長２．４５ＧＨｚ、出力５４０Ｗ）を２０分間照射し、反応終了後、反応液を濾過し、濾液を減圧下で除去し乾固させた。
0.5 g of cis-dichloro complex, 3.2 ml of TBAOH (10% aqueous solution) (2 mol of TBAOH with respect to 1 mol of cis-dichloro complex) and 0.86 g of TBASCN were simultaneously placed in a reaction vessel, and further N, N-
After the stirring, argon gas was passed through the solution for 10 minutes for deaeration, microwave irradiation (wavelength 2.45 GHz, output 540 W) was performed for 20 minutes under an argon atmosphere, and after completion of the reaction, the reaction solution was filtered, The filtrate was removed under reduced pressure to dryness.
その乾固後、残った固体を純水６０ｍｌに溶解し、得られた水溶液に希硝酸（０．５Ｎ）を２時間かけて滴下し、ｐＨ３．８に調整した。
このｐＨ調整により析出した固体を濾過器を用いて吸引濾過し、分離した固体を８時間真空乾燥した。
その後、乾燥物をアセトン３０ｍＬ、ジエチルエーテル１０ｍＬにて洗浄し、大気中にて７５℃で８時間乾燥した。
After the solidification, the remaining solid was dissolved in 60 ml of pure water, and diluted nitric acid (0.5 N) was added dropwise to the obtained aqueous solution over 2 hours to adjust the pH to 3.8.
The solid precipitated by this pH adjustment was suction filtered using a filter, and the separated solid was vacuum-dried for 8 hours.
Thereafter, the dried product was washed with 30 mL of acetone and 10 mL of diethyl ether, and dried in the air at 75 ° C. for 8 hours.
得られたＴＢＡ錯体を1Ｈ ＮＭＲ（Ｄ2Ｏ／ＮａＯＤ）で分析したところ、図２に示すように不純物を示すシグナルは検出されなかった。
なお、その際の収量は０．６８６ｇ、収率は７８％であった。
さらに、実施例１の場合と同様に、1Ｈ ＮＭＲ（Ｄ2Ｏ／ＮａＯＤ）の結果を解析し、目的の物質であることを確認した。
When the obtained TBA complex was analyzed by 1 H NMR (D 2 O / NaOD), no signal indicating impurities was detected as shown in FIG.
The yield at that time was 0.686 g, and the yield was 78%.
Further, in the same manner as in Example 1, the result of 1 H NMR (D 2 O / NaOD) was analyzed and confirmed to be the target substance.
［比較例１］
光を遮蔽した状態で１．１ｇ（１．７ｍｍｏｌ）のシス−ジクロロ錯体を５０ｍｌのＤＭＦに溶解する。
これとは別に準備した５．８２ｇ（６０ｍｍｏｌ）のＫＳＣＮを１０ｍｌの水に溶かし更に５０ｍｌのＤＭＦを追加したものとを混ぜ合わせ、その後溶液にアルゴンガスを通じ、更に攪拌しながら５時間還流する。
その際の反応生成物は、冷却した後グラスフィルターで濾過し、溶液からロータリーエバポレーターで溶媒を除去し、その除去後にＮａＯＨ(０．２Ｍ,２０ｍｌ)を加えることで暗赤紫色の溶液を得た。
[Comparative Example 1]
1.1 g (1.7 mmol) of cis-dichloro complex is dissolved in 50 ml of DMF with the light shielded.
Separately from this, 5.82 g (60 mmol) of KSCN dissolved in 10 ml of water and further added with 50 ml of DMF are mixed, and then the solution is refluxed for 5 hours while further stirring with argon gas.
The reaction product at that time was cooled and then filtered through a glass filter, the solvent was removed from the solution with a rotary evaporator, and NaOH (0.2 M, 20 ml) was added after the removal to obtain a dark red-purple solution. .
次いで、その溶液を濾過後、０．５Ｍの硝酸やトリフルオロメタンスルホン酸等の酸性溶液でｐＨを３．５以下にすることで沈殿を得た後、冷蔵庫で１２時間放置させ、その放置後、室温に戻してからグラスフィルターで吸引濾過し、固形物を集めた。
さらに、その固体を、先ほどと同じ酸を用いｐＨを３．５に調整した洗浄液で２０ｍｌ×３回洗浄した後、風乾したところ、収率は０．９ｇ(８５％)であった。
Then, after filtering the solution, a precipitate was obtained by adjusting the pH to 3.5 or less with an acidic solution such as 0.5 M nitric acid or trifluoromethanesulfonic acid, and then allowed to stand in the refrigerator for 12 hours. After returning to room temperature, suction filtration was performed with a glass filter, and the solid matter was collected.
Further, the solid was washed 20 ml × 3 times with a washing liquid adjusted to pH 3.5 using the same acid as described above, and then air-dried. The yield was 0.9 g (85%).
次に、上記化合物０．５ｇを蒸留水５０ｍｌに加えて溶解した溶液に１０％ＴＢＡＯＨ水溶液をｐＨが７に安定するまで滴下する。
この段階においてグラスフィルターで濾過し、濾液からロータリーエバポレーターで溶媒を除去し、除去後にメタノールを入れて溶かし、ジエチルエーテルと石油エーテルの混合液を加え沈殿物を得、その後２４時間真空乾燥を施した。
さらに、上記の化合物１ｇを蒸留水１０ｍｌに溶解し、０．１Ｍの硝酸溶液でｐＨを３．８以下にすると、沈殿が生ずるが、沈殿を取り出すまでの間、冷蔵庫に１２時間静置させておく。
その後、室温に戻しグラスフィルターで濾過し固液を分離した後，固体をｐＨ３．８の溶液５ｍｌで洗浄し、乾燥した。
Next, a 10% TBAOH aqueous solution is added dropwise to a solution obtained by adding 0.5 g of the above compound to 50 ml of distilled water and dissolving the solution until the pH is stabilized at 7.
At this stage, the solution was filtered through a glass filter, and the solvent was removed from the filtrate with a rotary evaporator. After removal, methanol was added to dissolve, and a precipitate was added by adding a mixture of diethyl ether and petroleum ether, followed by vacuum drying for 24 hours. .
Furthermore, when 1 g of the above compound is dissolved in 10 ml of distilled water and the pH is adjusted to 3.8 or less with a 0.1 M nitric acid solution, precipitation occurs, but it is allowed to stand in the refrigerator for 12 hours until the precipitate is removed. deep.
After returning to room temperature and filtering through a glass filter to separate the solid and liquid, the solid was washed with 5 ml of a pH 3.8 solution and dried.
得られたＴＢＡ錯体を、1Ｈ ＮＭＲ（Ｄ2Ｏ／ＮａＯＤ）で分析することで目的物を確認したところ、図３に示すようにごく僅かの異性体が検出された。
また、本発明の製造方法と比較して工程が煩雑で約３倍の時間を要した。
なお、その際の収量及び収率は０．６ｇ(８０％)であった。
そして、図３について更に解析すると、低磁場側に［Ｒｕ（ｄｃｂｐｙ）2（ＮＣＳ）（ＳＣＮ）］と思われる結合異性体のピークが若干不純物として検出されたものの目的の物質であることを確認した。
When the target product was confirmed by analyzing the obtained TBA complex by 1 H NMR (D 2 O / NaOD), only a few isomers were detected as shown in FIG.
Further, the process is complicated as compared with the production method of the present invention, and it takes about three times as much time.
The yield and yield at that time were 0.6 g (80%).
Further analysis with respect to FIG. 3 confirms that the peak of the bond isomer that appears to be [Ru (dcbpy) 2 (NCS) (SCN)] is detected as an impurity on the low magnetic field side, but is the target substance. did.
Claims (4)
After the reaction with tetra (n-butyl) ammonium thiocyanate, the solution was concentrated under reduced pressure, and the resulting solid material was dissolved or suspended in water. The resulting aqueous solution or suspension was diluted with dilute nitric acid solution to pH 3.0-4. The cis-bis (2,2′-bipyridine-4,4′-dicarboxylate-N, N ′ according to claim 1, 2 or 3, which is adjusted to 1. ) A process for producing bis [tetra (n-butyl) ammonium] bis (thiocyanato-N) ruthenium (II) acid.
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| JP2010277911A (en) * | 2009-05-29 | 2010-12-09 | Panasonic Electric Works Co Ltd | Dye-sensitized photoelectric conversion element |
| US8618294B2 (en) | 2010-07-09 | 2013-12-31 | Samsung Sdi Co., Ltd. | Dye for dye-sensitized solar cells, method of preparing the same, and solar cell including the dye |
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| JP2010277911A (en) * | 2009-05-29 | 2010-12-09 | Panasonic Electric Works Co Ltd | Dye-sensitized photoelectric conversion element |
| US8618294B2 (en) | 2010-07-09 | 2013-12-31 | Samsung Sdi Co., Ltd. | Dye for dye-sensitized solar cells, method of preparing the same, and solar cell including the dye |
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