JP2005255621A - Lariat type macrocyclic compound and metal complex and method for producing the same - Google Patents
Lariat type macrocyclic compound and metal complex and method for producing the same Download PDFInfo
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- JP2005255621A JP2005255621A JP2004069872A JP2004069872A JP2005255621A JP 2005255621 A JP2005255621 A JP 2005255621A JP 2004069872 A JP2004069872 A JP 2004069872A JP 2004069872 A JP2004069872 A JP 2004069872A JP 2005255621 A JP2005255621 A JP 2005255621A
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- 150000002678 macrocyclic compounds Chemical class 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 40
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 28
- 125000005843 halogen group Chemical group 0.000 claims abstract description 25
- 150000003141 primary amines Chemical class 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- -1 dialdehyde compound Chemical class 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 9
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052691 Erbium Inorganic materials 0.000 claims description 7
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 229910052775 Thulium Inorganic materials 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 7
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 7
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 7
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 7
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical class OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 150000002466 imines Chemical class 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000002000 scavenging effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000007022 RNA scission Effects 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- DYOBTPTUHDTANY-UHFFFAOYSA-K gadolinium(3+);trifluoromethanesulfonate Chemical compound [Gd+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F DYOBTPTUHDTANY-UHFFFAOYSA-K 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003579 shift reagent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
本発明は、大環状化合物及びその製造方法に関し、大環状化合物は、無機物、有機物、金属イオン等に対するホストとして働き、それらの分子あるいはイオンを環状の分子内に取り込むことができる機能性分子として注目されている。大環状化合物による取り込み能力を利用することにより、特定の物質に対する分離・精製剤や特定の物質に対するセンサーなどの応用が可能である。 The present invention relates to a macrocyclic compound and a method for producing the same, and the macrocyclic compound serves as a host for inorganic substances, organic substances, metal ions, and the like, and attracts attention as a functional molecule capable of incorporating those molecules or ions into a cyclic molecule. Has been. By utilizing the uptake ability of macrocyclic compounds, applications such as separation / purification agents for specific substances and sensors for specific substances are possible.
大環状化合物が金属イオンを取り込んだ金属錯体は、機能性分子としてさまざまな応用が可能である。外部磁場を増大させることなくＮＭＲ化学シフトを広げる目的で添加する常磁性金属イオン試薬であるシフト試薬は、主に希土類金属イオンからなる化合物であり、希土類金属イオンと大環状化合物からなる錯体が知られている。又，大環状化合物の金属錯体は、蛍光プローブや蛍光ラベル剤としても役立っている。さらにＲＮＡの開裂触媒としても使用されている。また１分子内に複数の金属イオンを有する大環状化合物は、金属間の隙間を利用した有機分子に対するホスト化合物として、さらにホスト−ゲスト反応を利用したセンサー機能の発現に期待が寄せられている。又、リン酸エステル加水分解酵素などが知られており、銅と希土類金属の双方が有機構造体中に組み込まれた構造のものがモデル化合物として報告されている等、大環状化合物の特許は数多く存在するが、一級アミンを持つラリアート型の大環状化合物およびその金属錯体、さらにはラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物及びその多核金属錯体に関する特許等は見当たらない（特許文献１〜３参照）。
また、学術文献については、ラリアート型の大環状化合物とその金属錯体に関する報告例はあるが、一級アミンを持つラリート型の大環状化合物を合成しているが（非特許文献１〜３参照）、それを複数個つないで、複数の環を持つ大環状化合物及びその多核金属錯体の合成に至る報告はない。
As for academic literature, there are reports on lariate-type macrocycles and their metal complexes, but we have synthesized ralito-type macrocycles with primary amines (see Non-Patent Documents 1 to 3), There is no report that connects a plurality of them to the synthesis of a macrocyclic compound having a plurality of rings and a polynuclear metal complex thereof.
従来、大環状化合物の複核金属錯体は、中心の金属イオン同士の相互作用や周りの配位子との相互作用が期待されており、単核錯体にはないユニークな蛍光特性や磁性特性を有している化合物があるのではないかということが期待されてきた。しかし、ほとんどの大環状化合物は、環のサイズや環内部の配位原子数の制限により、二個以上の金属イオンを捕捉することは難しく、たとえできたとしても従来の研究によれば、このような化合物は特定の金属イオンを鋳型にして合成されているために金属イオンの選択が困難である。また目的物として配位させた配位子以外の配位子が配位することが起こり、期待されている特性が阻害されたり、場合によっては加水分解が起こり、金属イオンが配位子から抜け落ちるなどの問題があった。また錯体が有しているであろうと考えられる機能を十分に引き出すことは困難であった。
本発明では、先端に一級アミンを有するラリアート型大環状化合物を合成し、環の内部には、金属イオンを捕捉するためにイミンあるいはアミン、水酸基等からなる複数個の配位部位が存在しており、単核錯体の合成ができるラリアート型大環状化合物及びその製造方法を提供する。
Conventionally, macrocyclic binuclear metal complexes are expected to interact with central metal ions and with surrounding ligands, and have unique fluorescence and magnetic properties not found in mononuclear complexes. There has been an expectation that there may be compounds that do this. However, most macrocycles are difficult to trap two or more metal ions due to the limitations of the ring size and the number of coordination atoms inside the ring. Since such a compound is synthesized using a specific metal ion as a template, it is difficult to select the metal ion. In addition, ligands other than the ligand coordinated as the target substance may be coordinated, and the expected properties may be impaired, or hydrolysis may occur in some cases, causing metal ions to fall out of the ligand. There were problems such as. Moreover, it was difficult to fully extract the functions that the complex would have.
In the present invention, a lariat-type macrocyclic compound having a primary amine at the tip is synthesized, and a plurality of coordination sites consisting of imine, amine, hydroxyl group, etc. are present inside the ring to capture metal ions. The present invention provides a lariat-type macrocycle capable of synthesizing a mononuclear complex and a method for producing the same.
本発明は、
化学式
一般式（Ｖ）
で表わされるジアルデヒド化合物を、溶媒中で、不活性ガス雰囲気下、５０〜８０℃で反応させることにより一般式（I）
で表わされる一級アミンを持つラリアート型大環状化合物を得る。
また、
一般式（I）
で表わされる一級アミンを持つラリアート型大環状化合物を溶剤に溶解し、金属塩の溶液と反応させることにより、
一般式（II）
で表わされる一級アミンを持つラリアート型大環状化合物錯塩を得る。
さらに、本発明は、
一般式（I）
で表わされる一級アミンを持つラリアート型大環状化合物と、一般式（Ｖ）
で表わされるジアルデヒド化合物を、溶媒中で、不活性ガス雰囲気下、５０〜８０℃で反応させることにより、一般式（III）
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物を得る。
さらにまた、
一般式（III）
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物を、を溶剤に溶解し、金属塩の溶液と反応させることにより、
一般式（IV）
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物の多核金属錯体を得る。
The present invention
Chemical formula
Is reacted in a solvent in an inert gas atmosphere at 50 to 80 ° C. to obtain the general formula (I)
A lariat-type macrocyclic compound having a primary amine represented by the formula is obtained.
Also,
Formula (I)
By dissolving a lariat-type macrocyclic compound having a primary amine represented by the following formula in a solvent and reacting with a metal salt solution:
Formula (II)
A lariat-type macrocyclic compound complex salt having a primary amine represented by the formula is obtained.
Furthermore, the present invention provides
Formula (I)
A lariat-type macrocyclic compound having a primary amine represented by the general formula (V)
Is reacted in a solvent in an inert gas atmosphere at 50 to 80 ° C., to thereby obtain a compound represented by the general formula (III)
A macrocyclic compound having a plurality of rings obtained by connecting a plurality of lariat-type macrocyclic compounds having a primary amine represented by the formula:
Furthermore,
General formula (III)
By dissolving a macrocycle having a plurality of rings in which a plurality of lariat-type macrocycles having a primary amine represented by the formula shown above are dissolved in a solvent and reacting with a solution of a metal salt,
Formula (IV)
A polynuclear metal complex of a macrocyclic compound having a plurality of rings obtained by connecting a plurality of lariat-type macrocyclic compounds having a primary amine represented by
本発明のラリアート型大環状化合物は、環の内部に金属イオンへの配位部位を持つことから、環の数に応じた二核あるいは三核錯体の創製が可能である。このように逐次反応により、１分子内に複数の金属イオンを持つ多核錯体を創製することが可能となる。
これらのラリアート型大環状化合物あるいは単核の金属錯体が有する先端の一級アミンを反応させることにより、複数の環を持つ大環状化合物及びその多核金属錯体の創製が可能となる。
Since the lariat-type macrocyclic compound of the present invention has a coordination site to a metal ion inside the ring, it is possible to create a binuclear or trinuclear complex depending on the number of rings. In this way, it is possible to create a polynuclear complex having a plurality of metal ions in one molecule by successive reactions.
By reacting the leading primary amine of these lariat-type macrocyclic compounds or mononuclear metal complexes, it is possible to create macrocycle compounds having a plurality of rings and polynuclear metal complexes thereof.
本発明において用いることができるジアルデヒド化合物は、一般式中、R1, R2は、塩素、臭素などのハロゲン原子、メチル基、エチル基などの低級アルキル基、メトキシ基、tert-ブチル基などの分岐上低級アルキル基より選ばれる1種であり、R1,R2は、同一であっても異なっていても良い。
また、溶媒としては、メタノール、エタノール、プロパノール等のアルコール類とくに脱水メタノールが好ましい。用いる不活性ガスとしては、窒素、ヘリウム、ネオン、アルゴン等が挙げられる。
また、反応温度は、１０〜８０℃で反応させる。
本発明の金属錯体おいて、用いることが出来る金属は、スカンジウム、イットリウム、ランタン、セリウム、プラセオジム、ネオジウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムからなる群れより成る希土類金属の1種の金属イオン、または、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛からなる群れより選ばれる金属イオンの1種である。
The dialdehyde compound that can be used in the present invention is represented by the general formula: R 1 and R 2 are halogen atoms such as chlorine and bromine, lower alkyl groups such as methyl and ethyl groups, methoxy groups, tert-butyl groups and the like. It is one selected from upper and lower alkyl groups, and R1 and R2 may be the same or different.
As the solvent, alcohols such as methanol, ethanol and propanol, particularly dehydrated methanol is preferable. Examples of the inert gas used include nitrogen, helium, neon, and argon.
The reaction temperature is 10 to 80 ° C.
The metal that can be used in the metal complex of the present invention is a group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. One kind of metal ion selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, and zinc.
実施例１
トリス（２−アミノエチル）アミン１．８ミリモルを脱水メタノール３６０ミリリットルと脱水ＤＭＦ１８０ミリリットルの混合溶媒に溶かし、窒素気流下、７０度で撹拌しながら、ジアルデヒド化合物（Ｒ１＝水素、Ｒ２＝水素）１．８ミリモルを含む脱水メタノール９０ミリリットルを１時間かけて滴下により加えた。その後、３０分間、撹拌を続けた。
３０度に温度を下げて、水素化ホウ素ナトリウムを反応溶液の黄色が消えるまで少しずつ加えた。溶液をろ過した後、溶媒を減圧留去した。これに塩化メチレンを加えて有機層を水で３〜４回洗浄した。有機層を硫酸マグネシウムで乾燥した後、ろ過を行った。その後、塩化メチレンを減圧留去して白色の固体を得た。
得られた固体をクロロホルムに溶かして、アミノプロピル化したシリカゲルを用いたカラムにより分離精製して目的物を得た。収率は６７％であった。
得られた個体をアセトニトリルに溶かして、ESI-MSを測定した結果、m/z, 411.3（+H+で、計算値が411.3）にピークが観測された。元素分析値は、C24.5H35.5N4O2.5Na0.5=437.56（1/2メタノールと1/2-ONa(-OHに代わって)を含む）に対して、C,67.15%（計算値67.25%）、 H,8.07%（計算値8.18）、N,12.66%（計算値12.80%）となった。IR(KBrディスク)では、3414,3362, 3294, 3065, 2906, 2837, 1643, 1591, 1458, 1263, 1216, 1159, 1107, 1076,887, 846, 754 cm-1にピークが観測された。以上の結果から、目的物（一般式IのＲ１＝水素、Ｒ２＝水素）であることを確認した。
Example 1
Dissolve 1.8 mmol of tris (2-aminoethyl) amine in a mixed solvent of 360 ml of dehydrated methanol and 180 ml of dehydrated DMF, and stir at 70 degrees under a nitrogen stream while dialdehyde compound (R1 = hydrogen, R2 = hydrogen). 90 ml of dehydrated methanol containing 1.8 mmol was added dropwise over 1 hour. Thereafter, stirring was continued for 30 minutes.
The temperature was lowered to 30 degrees and sodium borohydride was added in small portions until the yellow color of the reaction solution disappeared. After filtering the solution, the solvent was distilled off under reduced pressure. Methylene chloride was added thereto, and the organic layer was washed 3 to 4 times with water. The organic layer was dried over magnesium sulfate and then filtered. Thereafter, methylene chloride was distilled off under reduced pressure to obtain a white solid.
The obtained solid was dissolved in chloroform and separated and purified by a column using aminopropylated silica gel to obtain the desired product. The yield was 67%.
The obtained solid was dissolved in acetonitrile and measured for ESI-MS. As a result, a peak was observed at m / z, 411.3 (+ H + , calculated value: 411.3). Elemental analysis values are C 24.5 H 35.5 N 4O2.5 Na 0.5 = 437.56 (including 1/2 methanol and 1 / 2-ONa (instead of -OH)), C, 67.15% (calculated value 67.25 %), H, 8.07% (calculated value 8.18), N, 12.66% (calculated value 12.80%). In IR (KBr disk), peaks were observed at 3414, 3362, 3294, 3065, 2906, 2837, 1643, 1591, 1458, 1263, 1216, 1159, 1107, 1076, 887, 846, and 754 cm- 1 . From the above results, it was confirmed that the target product (R1 = hydrogen, R2 = hydrogen in general formula I) was obtained.
実施例１で得た化合物０．１ミリモルを脱水メタノール１５ミリリットルとクロロホルム１５ミリリットルの混合溶媒に溶かし、これにトリエチルアミン０．２ミリモルを加えて、さらに塩化コバルト０．１ミリモルを溶かした脱水メタノール１５ミリリットルを加えた。反応溶液を１時間、加熱還流した後、メタノールを自然蒸発させたところ紫色の析出物が得られた。収率は５５％であった。
得られた個体をアセトニトリルに溶かして、ESI-MSを測定した結果、m/z, 467.1（[CoIII(C24H32N4O2)+]で、計算値が467.2）にピークが観測された。IR(KBrディスク)では、3227,2936, 2677, 1631, 1592, 1448, 1265, 1049, 894, 856, 763, 595, 551, 512 cm-1にピークが観測された。以上の結果から、目的物（一般式IのＲ１＝水素、Ｒ２＝水素コバルト錯体）であることを確認した。
0.1 mmol of the compound obtained in Example 1 was dissolved in a mixed solvent of 15 ml of dehydrated methanol and 15 ml of chloroform, 0.2 mmol of triethylamine was added thereto, and dehydrated methanol 15 containing 0.1 mmol of cobalt chloride was further dissolved. Milliliter was added. The reaction solution was heated to reflux for 1 hour and then the methanol was naturally evaporated to obtain a purple precipitate. The yield was 55%.
The obtained solid was dissolved in acetonitrile, and ESI-MS was measured. As a result, a peak was observed at m / z, 467.1 ([Co III (C 24 H 32 N 4 O 2 ) + ], calculated value 467.2). It was done. In IR (KBr disk), peaks were observed at 3227,2936, 2677, 1631, 1592, 1448, 1265, 1049, 894, 856, 763, 595, 551, 512 cm -1 . From the above results, it was confirmed that it was the target product (R1 = hydrogen, R2 = hydrogen cobalt complex of general formula I).
実施例３
実施例１で得た化合物０．１ミリモルを脱水メタノール１５ミリリットルとクロロホルム１５ミリリットルの混合溶媒に溶かし、これにトリエチルアミン０．２ミリモルを加えて、さらに酢酸ニッケル０．１モルを溶かした脱水メタノール１５ミリリットルを加えた。メタノールを自然蒸発させたところ、青緑色の析出物が得られた。収率は４８％であった。
得られた個体をアセトニトリルに溶かして、ESI-MSを測定した結果、m/z, 467.2（[NiII(C24H32N4O2)+H+]で、計算値が467.2）にピークが観測された。IR(KBrディスク)では、3283,2979, 2923, 1577, 1446, 1293, 1212, 1080, 1018, 924,885，852, 757, 654, 547, 455cm-1にピークが観測された。以上の結果から、目的物（一般式IのＲ１＝水素、Ｒ２＝水素のニッケル錯体）であることを確認した。
Example 3
0.1 mmol of the compound obtained in Example 1 was dissolved in a mixed solvent of 15 ml of dehydrated methanol and 15 ml of chloroform, 0.2 mmol of triethylamine was added to this, and dehydrated methanol 15 in which 0.1 mol of nickel acetate was further dissolved. Milliliter was added. When methanol was naturally evaporated, a blue-green precipitate was obtained. The yield was 48%.
The obtained solid was dissolved in acetonitrile, and ESI-MS was measured. As a result, it peaked at m / z, 467.2 ([Ni II (C 24 H 32 N 4 O 2 ) + H + ], calculated value 467.2). Was observed. In IR (KBr disk), peaks were observed at 3283, 2979, 2923, 1577, 1446, 1293, 1212, 1080, 1018, 924,885, 852, 757, 654, 547, and 455 cm- 1 . From the above results, it was confirmed that it was the target product (R1 = hydrogen in general formula I, R2 = nickel complex of hydrogen).
実施例１で得られた化合物０．２ミリモルを脱水メタノール６０ミリリットルと脱水ＤＭＦ３０ミリリットルの混合溶媒に溶かし、窒素気流下、７０度で撹拌しながら、ジアルデヒド化合物（Ｒ１＝水素、Ｒ２＝水素）０．１ミリモルを含む脱水メタノール２０ミリリットルを３０分かけて滴下により加えた。その後、１時間、撹拌を続けた。
３０度に温度を下げて、水素化ホウ素ナトリウムを反応溶液の黄色が消えるまで少しずつ加えた。溶液をろ過した後、溶媒を減圧留去した。これに塩化メチレンを加えて有機層を水で３〜４回洗浄した。有機層を硫酸マグネシウムで乾燥した後、ろ過を行った。その後、塩化メチレンを減圧留去して白色の固体を得た。
得られた固体をクロロホルムに溶かして、アミノプロピル化したシリカゲルを用いたカラムにより分離精製して目的物（一般式IIIのＲ１＝水素、Ｒ２＝水素）を得た。収率は６０％であった。
得られた個体をアセトニトリルに溶かして、ESI-MSを測定した結果、m/z, 1084.6（+H+で、計算値が1084.6）にピークが観測された。元素分析値は、C66H84N8O6・CH3OH=1117.47に対して、C,71.89%（計算値72.01%）、H,7.99%（計算値7.94）、N,10.22%（計算値10.03%）となった。IR(KBrディスク)では、2918, 2848, 1641, 1595.1460, 1386, 1259, 1079, 879, 753, 603, 465 cm-1にピークが観測された。以上の結果から、目的物（一般式IIIのＲ１＝水素、Ｒ２＝水素）であることを確認した。
0.2 mmol of the compound obtained in Example 1 was dissolved in a mixed solvent of 60 ml of dehydrated methanol and 30 ml of dehydrated DMF, and the dialdehyde compound (R1 = hydrogen, R2 = hydrogen) was stirred at 70 degrees under a nitrogen stream. 20 ml of dehydrated methanol containing 0.1 mmol was added dropwise over 30 minutes. Thereafter, stirring was continued for 1 hour.
The temperature was lowered to 30 degrees and sodium borohydride was added in small portions until the yellow color of the reaction solution disappeared. After filtering the solution, the solvent was distilled off under reduced pressure. Methylene chloride was added thereto, and the organic layer was washed 3 to 4 times with water. The organic layer was dried over magnesium sulfate and then filtered. Thereafter, methylene chloride was distilled off under reduced pressure to obtain a white solid.
The obtained solid was dissolved in chloroform and separated and purified by a column using aminopropylated silica gel to obtain the desired product (R1 = hydrogen, R2 = hydrogen in general formula III). The yield was 60%.
The obtained solid was dissolved in acetonitrile, and ESI-MS was measured. As a result, a peak was observed at m / z, 1084.6 (+ H + , calculated value was 1084.6). The elemental analysis values are C, 71.89% (calculated value 72.01%), H, 7.99% (calculated value 7.94), N, 10.22% (calculated) for C 66 H 84 N 8 O 6 · CH 3 OH = 1117.47 Value 10.03%). In IR (KBr disk), peaks were observed at 2918, 2848, 1641, 1595.1460, 1386, 1259, 1079, 879, 753, 603, and 465 cm- 1 . From the above results, it was confirmed that it was the target product (R1 = hydrogen, R2 = hydrogen in general formula III).
実施例４で得た化合物０．１ミリモルを脱水メタノール２０ミリリットルとクロロホルム１０ミリリットルの混合溶媒に溶かし、これにトリエチルアミン０．６ミリモルを加えて、さらにユウロピウムの塩であるユウロピウムトリフラート０．２ミリモルを溶かした脱水メタノール２０ミリリットルを加えた。メタノールを自然蒸発させたところ、淡黄色の結晶が得られた。収率は３５％であった。
得られた個体をアセトニトリルに溶かして、ESI-MSを測定した結果、m/z, 1383.2（+H+で、計算値が1383.4）及び1405.1（+Na+で、計算値が1405.4）にピークが観測された。
以上の結果から、目的物（一般式IIIのＲ１＝水素、Ｒ２＝水素のユウロピウムの複核錯体）であることを確認した。
0.1 mmol of the compound obtained in Example 4 was dissolved in a mixed solvent of 20 ml of dehydrated methanol and 10 ml of chloroform. 20 milliliters of dissolved dehydrated methanol was added. When the methanol was naturally evaporated, pale yellow crystals were obtained. The yield was 35%.
The obtained solid was dissolved in acetonitrile, and ESI-MS was measured. As a result, peaks were observed at m / z, 1383.2 (+ H + , calculated value 1383.4) and 1405.1 (+ Na + , calculated value 1405.4). Observed.
From the above results, it was confirmed that it was the target product (R1 = hydrogen, R2 = hydrogen europium complex of general formula III).
実施例４で得た化合物０．１ミリモルを脱水メタノール２０ミリリットルとクロロホルム１０ミリリットルの混合溶媒に溶かし、これにトリエチルアミン０．６ミリモルを加えて、さらにガドリニウムの塩であるガドリニウムトリフラート０．２ミリモルを溶かした脱水メタノール２０ミリリットルを加えた。メタノールを自然蒸発させたところ、淡黄色の結晶が得られた。収率は３３％であった。
得られた個体をアセトニトリルに溶かして、ESI-MSを測定した結果、m/z, 1397.1（+H+で、計算値が1397.4）及び1419.1（+Na+で、計算値が1419.4）にピークが観測された。
以上の結果から、目的物（一般式IIIのＲ１＝水素、Ｒ２＝水素のガドリニウムの複核錯体）であることを確認した。
0.1 mmol of the compound obtained in Example 4 was dissolved in a mixed solvent of 20 ml of dehydrated methanol and 10 ml of chloroform, and 0.6 mmol of triethylamine was added thereto, and further 0.2 mmol of gadolinium triflate which is a salt of gadolinium was added. 20 milliliters of dissolved dehydrated methanol was added. When the methanol was naturally evaporated, pale yellow crystals were obtained. The yield was 33%.
The obtained solid was dissolved in acetonitrile, and ESI-MS was measured. As a result, peaks were found at m / z, 1397.1 (+ H + , calculated value 1397.4) and 1419.1 (+ Na + , calculated value 1419.4). Observed.
From the above results, it was confirmed that the product was the target product (R1 = hydrogen, R2 = hydrogen gadolinium complex of general formula III).
実施例５で得られた結晶のＸ線結晶構造解析を行った結果、得られた化合物は、１分子内に２個の大環状部位を有しており、それぞれの環が１個のユウロピウムイオンを内包した複核錯体であることを確認した。それぞれのユウロピウムイオンには、４個の窒素原子と３個の酸素原子が配位しており、それ以外の陰イオンや溶媒分子は配位していないことを確認した。 As a result of X-ray crystal structure analysis of the crystal obtained in Example 5, the obtained compound has two macrocyclic sites in one molecule, and each ring has one europium ion. It was confirmed that it was a binuclear complex encapsulating. It was confirmed that each europium ion was coordinated with 4 nitrogen atoms and 3 oxygen atoms, and other anions and solvent molecules were not coordinated.
実施例５で得られた結晶をメタノールに溶かし、これに塩化セシウムのメタノール溶液を添加した後、アセトニトリルで希釈して、ESI-MSを測定した結果、ユウロピウムの複核錯体：セシウムイオン＝１：１に対応するピークが、m/z, 1515.1（計算値が1515.3）に観測された。このことからユウロピウムの複核錯体は、セシウムイオンに対して、ホストとして機能していることを確認した。 The crystal obtained in Example 5 was dissolved in methanol, a methanol solution of cesium chloride was added thereto, and then diluted with acetonitrile, and ESI-MS was measured. As a result, europium dinuclear complex: cesium ion = 1: 1. A peak corresponding to is observed at m / z, 1515.1 (calculated value is 1515.3). From this, it was confirmed that the europium binuclear complex functions as a host for cesium ions.
大環状化合物による取り込み能力を利用することにより、特定の物質に対する分離・精製剤や特定の物質に対するセンサーとして応用が可能である。
また１分子内に複数の金属イオンを有する大環状化合物は、金属間の隙間を利用した特定の物質に対するホスト化合物として、さらにホスト−ゲスト反応を利用したセンサー機能の発現に期待が寄せられている。大環状化合物の複核金属錯体は、中心の金属イオン同士の相互作用や周りの配位子との相互作用が期待されており、単核錯体にはないユニークな蛍光特性や磁性特性を有している化合物があるのではないかということが期待されており、そういった性質を応用した各種の蛍光材料、磁性材料への応用が期待される。
By utilizing the uptake ability of the macrocyclic compound, it can be applied as a separation / purification agent for a specific substance or a sensor for a specific substance.
Macrocycles having a plurality of metal ions in one molecule are expected to develop sensor functions using host-guest reactions as host compounds for specific substances using gaps between metals. . Macrocyclic binuclear metal complexes are expected to interact with central metal ions and with surrounding ligands, and have unique fluorescence and magnetic properties not found in mononuclear complexes. It is expected that there may be some compounds, and application to various fluorescent materials and magnetic materials applying such properties is expected.
Claims (8)
で表わされる一級アミンを持つラリアート型大環状化合物。 Formula (I)
A lariat-type macrocyclic compound having a primary amine represented by
で表わされる一級アミンを持つラリアート型大環状化合物錯塩。 Formula (II)
A lariat-type macrocyclic compound complex salt having a primary amine represented by
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物。 General formula (III)
A macrocycle having a plurality of rings in which a plurality of lariat-type macrocycles having a primary amine represented by
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物の多核金属錯体。 Formula (IV)
A polynuclear metal complex of a macrocycle having a plurality of rings in which a plurality of lariat-type macrocycles having a primary amine represented by
一般式（Ｖ）
で表わされるジアルデヒド化合物を、溶媒中で、不活性ガス雰囲気下、５０〜８０℃で反応させる一般式（I）
で表わされる一級アミンを持つラリアート型大環状化合物の製造方法。
Chemical formula
A general formula (I) in which a dialdehyde compound represented by formula (I) is reacted in a solvent at 50 to 80 ° C. in an inert gas atmosphere.
A method for producing a lariat-type macrocyclic compound having a primary amine represented by the formula:
で表わされる一級アミンを持つラリアート型大環状化合物を溶剤に溶解し、金属塩の溶液と反応させる
一般式（II）
で表わされる一級アミンを持つラリアート型大環状化合物錯塩の製造方法。 Formula (I)
A general formula (II) in which a lariat-type macrocyclic compound having a primary amine represented by the formula is dissolved in a solvent and reacted with a metal salt solution.
The manufacturing method of the lariat type | mold macrocyclic complex salt which has the primary amine represented by these.
で表わされる一級アミンを持つラリアート型大環状化合物と、一般式（Ｖ）
で表わされるジアルデヒド化合物を、溶媒中で、不活性ガス雰囲気下、５０〜８０℃で反応させる一般式（III）
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物の製造方法。 Formula (I)
A lariat-type macrocyclic compound having a primary amine represented by the general formula (V)
A general formula (III) in which a dialdehyde compound represented by the formula is reacted in a solvent at 50 to 80 ° C. in an inert gas atmosphere.
A method for producing a macrocyclic compound having a plurality of rings in which a plurality of lariat-type macrocyclic compounds having a primary amine represented by
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物を、を溶剤に溶解し、金属塩の溶液と反応させる
一般式（IV）
で表わされる一級アミンを持つラリアート型大環状化合物を複数個つないだ複数の環を持つ大環状化合物の多核金属錯体の製造方法。
General formula (III)
A general formula (IV) in which a macrocyclic compound having a plurality of rings in which a plurality of lariat-type macrocyclic compounds having a primary amine represented by the formula is connected is dissolved in a solvent and reacted with a metal salt solution.
A method for producing a polynuclear metal complex of a macrocycle having a plurality of rings in which a plurality of lariat-type macrocycles having a primary amine represented by the formula are connected.
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