JP2011093854A - Terpyridyl-containing compound - Google Patents
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- JP2011093854A JP2011093854A JP2009250661A JP2009250661A JP2011093854A JP 2011093854 A JP2011093854 A JP 2011093854A JP 2009250661 A JP2009250661 A JP 2009250661A JP 2009250661 A JP2009250661 A JP 2009250661A JP 2011093854 A JP2011093854 A JP 2011093854A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004429 atom Chemical group 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000008204 material by function Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GGQCFEVXYDVISX-UHFFFAOYSA-N 1-iodo-4-[tris(4-iodophenyl)methyl]benzene Chemical compound C1=CC(I)=CC=C1C(C=1C=CC(I)=CC=1)(C=1C=CC(I)=CC=1)C1=CC=C(I)C=C1 GGQCFEVXYDVISX-UHFFFAOYSA-N 0.000 description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- QAHRKVOFOFJSMH-UHFFFAOYSA-N tetrakis(4-iodophenyl)silane Chemical compound C1=CC(I)=CC=C1[Si](C=1C=CC(I)=CC=1)(C=1C=CC(I)=CC=1)C1=CC=C(I)C=C1 QAHRKVOFOFJSMH-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(*)*c1cc(-c2ncccc2)nc(-c2ncccc2)c1 Chemical compound CC(C)(*)*c1cc(-c2ncccc2)nc(-c2ncccc2)c1 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
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- 239000012044 organic layer Substances 0.000 description 1
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- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004424 polypyridyl Polymers 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
Description
本発明は、新規なテルピリジル基含有化合物に関する。 The present invention relates to a novel terpyridyl group-containing compound.
従来、配位結合性化合物として、テルピリジル基を有する有機化合物に関する研究が精力的に行われている（下記特許文献１参照）。 Conventionally, studies on organic compounds having a terpyridyl group have been vigorously conducted as a coordination bond compound (see Patent Document 1 below).
配位子に金属が配位した金属錯体は、触媒材料やエネルギー変換材料等の機能性材料として注目されている。 Metal complexes in which a metal is coordinated to a ligand are attracting attention as functional materials such as catalyst materials and energy conversion materials.
ポリピリジル化合物は、種々の金属と錯体を形成し、エレクトロクロミズムや光触媒等の特異な性質を示す金属配位子として興味がもたれている。 Polypyridyl compounds are of interest as metal ligands that form complexes with various metals and exhibit unique properties such as electrochromism and photocatalysis.
しかし、既存の配位性有機化合物は、その複数の配位部位の方向性を保つことが難しいという課題があった。 However, the existing coordination organic compound has a problem that it is difficult to maintain the directionality of the plurality of coordination sites.
新規な構造を持つテルピリジル基含有化合物を得ることは、機能性材料の新たな展開の上で意味深いことである。そこで、本発明は、新規なテルピリジル基含有化合物を提供することを目的とする。 Obtaining a terpyridyl group-containing compound having a novel structure is significant in the new development of functional materials. Accordingly, an object of the present invention is to provide a novel terpyridyl group-containing compound.
上記目的を達成するために、本発明は、炭素原子又はケイ素原子を中心原子とし、該中心原子に結合した同一の有機基を４つ有し、上記有機基がそれぞれテルピリジル基を１つ含む基である、テルピリジル基含有化合物を提供する。 In order to achieve the above object, the present invention provides a group having four identical organic groups bonded to the central atom with a carbon atom or silicon atom as the central atom, and each of the organic groups includes one terpyridyl group. A terpyridyl group-containing compound is provided.
本発明のテルピリジル基含有化合物は、新規な構造を有する有機化合物であり、中心に炭素又はケイ素を持つため、立体的な構造をとり、配位部位の異方性を持つ。また、本発明のテルピリジル基含有化合物は、４つのテルピリジル基を持つため、複数の金属を結合させることができる。ここでテルピリジル基は、その芳香環に置換基を有するものも含む。 The terpyridyl group-containing compound of the present invention is an organic compound having a novel structure and has carbon or silicon at the center, and thus has a three-dimensional structure and has anisotropy in the coordination site. Moreover, since the terpyridyl group-containing compound of the present invention has four terpyridyl groups, it can bind a plurality of metals. Here, the terpyridyl group includes those having a substituent on the aromatic ring.
本発明のテルピリジル基含有化合物は、芳香環を有する化合物であることが好ましい。テルピリジル基含有化合物が芳香環を有することにより、分子の剛直性が得られ、大きな分子サイズを得ることができる。 The terpyridyl group-containing compound of the present invention is preferably a compound having an aromatic ring. When the terpyridyl group-containing compound has an aromatic ring, molecular rigidity can be obtained and a large molecular size can be obtained.
本発明のテルピリジル基含有化合物は、下記一般式（１）で表される化合物であることが好ましい。
［式（１）中、Ｘは炭素原子又はケイ素原子を示し、Ｙは単結合、或いは、下記一般式（２）又は（３）で表される基を示す。］
［式（２）中、Ｒ１は水素原子、メチル基、エチル基又はフェニル基を示し、Ｒ２及びＲ３はそれぞれ独立に水素原子、メチル基又はエチル基を示し、ｎは１又は２を示す。］
［式（３）中、Ｒ４は水素原子、メチル基又はエチル基を示し、ｍは１〜３の整数を示す。］
The terpyridyl group-containing compound of the present invention is preferably a compound represented by the following general formula (1).
[In the formula (1), X represents a carbon atom or a silicon atom, and Y represents a single bond or a group represented by the following general formula (2) or (3). ]
[In the formula (2), R 1 represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, R 2 and R 3 each independently represent a hydrogen atom, a methyl group or an ethyl group, and n represents 1 or 2 Show. ]
[In formula (3), R 4 represents a hydrogen atom, a methyl group or an ethyl group, m is an integer of 1-3. ]
上記一般式（１）で表されるテルピリジル基含有化合物は、構造の立体性、配位部位の異方性、及び、４つのテルピリジル基により複数の金属を結合させる効果をより向上させることができる。 The terpyridyl group-containing compound represented by the general formula (1) can further improve the stericity of the structure, the anisotropy of the coordination site, and the effect of bonding a plurality of metals by four terpyridyl groups. .
本発明のテルピリジル基含有化合物は、カップリング反応により合成される化合物であることが好ましい。カップリング反応により合成されたテルピリジル基含有化合物は、より安定した特性を得ることができる。 The terpyridyl group-containing compound of the present invention is preferably a compound synthesized by a coupling reaction. The terpyridyl group-containing compound synthesized by the coupling reaction can obtain more stable characteristics.
本発明によれば、新規なテルピリジル基含有化合物を提供することができる。本発明のテルピリジル基含有化合物は、中心に炭素又はケイ素を持つため、立体的な構造をとり、配位部位の異方性を持つ。また、本発明のテルピリジル基含有化合物は、分子内に芳香環を有する場合、剛直性が得られ、大きな分子サイズが得られる。 According to the present invention, a novel terpyridyl group-containing compound can be provided. Since the terpyridyl group-containing compound of the present invention has carbon or silicon at the center, it takes a three-dimensional structure and has anisotropy of the coordination site. Moreover, when the terpyridyl group-containing compound of the present invention has an aromatic ring in the molecule, rigidity is obtained and a large molecular size is obtained.
また、本発明のテルピリジル基含有化合物は、４つのテルピリジル基を持つため、複数の金属を結合させることができる。 Moreover, since the terpyridyl group-containing compound of the present invention has four terpyridyl groups, it can bind a plurality of metals.
本発明のテルピリジル基含有化合物の用途として、例えば、水素吸蔵材料への使用が挙げられる。本発明のテルピリジル基含有化合物を、水素を化学吸着する金属微粒子と組み合わせることで、物理吸着サイトとなりうる規則的なフレームワーク構造を持つ水素吸蔵材料を得ることができる。 The use of the terpyridyl group-containing compound of the present invention includes, for example, use in a hydrogen storage material. By combining the terpyridyl group-containing compound of the present invention with metal fine particles that chemically adsorb hydrogen, a hydrogen storage material having a regular framework structure that can serve as a physical adsorption site can be obtained.
また、本発明のテルピリジル基含有化合物の他の用途として、例えば、触媒材料への使用が挙げられる。本発明のテルピリジル基含有化合物を、触媒能を持つ金属イオンと組み合わせることで、特異な選択性を持つ触媒を得ることができる。 Moreover, the use as a catalyst material is mentioned as another use of the terpyridyl group containing compound of this invention, for example. A catalyst having specific selectivity can be obtained by combining the terpyridyl group-containing compound of the present invention with a metal ion having catalytic ability.
更に、本発明のテルピリジル基含有化合物の他の用途として、例えば、電子移動媒体への使用が挙げられる。本発明のテルピリジル基含有化合物を、光応答性を持つ金属イオンと組み合わせることで、新規なエネルギー材料を得ることができる。 Furthermore, other uses of the terpyridyl group-containing compound of the present invention include, for example, use in an electron transfer medium. A novel energy material can be obtained by combining the terpyridyl group-containing compound of the present invention with a metal ion having photoresponsiveness.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本発明のテルピリジル基含有化合物は、炭素原子又はケイ素原子を中心原子とし、該中心原子に結合した同一の有機基を４つ有し、上記有機基がそれぞれテルピリジル基を１つ含む基である化合物である。中心原子に結合した４つの有機基がそれぞれ１つのテルピリジル基を含むため、テルピリジル基含有化合物は分子内に４つのテルピリジル基を有することとなる。 The terpyridyl group-containing compound of the present invention has a carbon atom or silicon atom as a central atom, has four identical organic groups bonded to the central atom, and each of the organic groups is a group containing one terpyridyl group It is. Since each of the four organic groups bonded to the central atom contains one terpyridyl group, the terpyridyl group-containing compound has four terpyridyl groups in the molecule.
上記テルピリジル基含有化合物は、テルピリジル基において金属微粒子と配位結合により結合しやすく、安定した結合状態を得ることができる。 The terpyridyl group-containing compound can be easily bonded to the metal fine particle by a coordinate bond in the terpyridyl group, and a stable bonded state can be obtained.
また、上記テルピリジル基含有化合物において、４つテルピリジル基は金属への修飾に異方性を持つため、金属微粒子とテルピリジル基含有化合物とが交互に結合した３次元網目構造を形成しやすい。ここで、テルピリジル基含有化合物は、中心に炭素又はケイ素を持つことによりテルピリジル基の異方性が生じ、テトラヘドラルな対称性を持つこととなる。また、それらの効果がより有効に奏されることから、テルピリジル基含有化合物において、有機基は末端にテルピリジル基を有していることが好ましい。 Further, in the terpyridyl group-containing compound, since the four terpyridyl groups have anisotropy in the modification to the metal, it is easy to form a three-dimensional network structure in which the metal fine particles and the terpyridyl group-containing compound are alternately bonded. Here, the terpyridyl group-containing compound has carbon or silicon at the center, so that the anisotropy of the terpyridyl group is generated and has tetrahedral symmetry. Moreover, since those effects are more effectively exhibited, in the terpyridyl group-containing compound, the organic group preferably has a terpyridyl group at the terminal.
上記テルピリジル基含有化合物は、分子内に芳香環を有する化合物であることが好ましい。芳香環を有することでテルピリジル基含有化合物の分子の剛直性が増す。また、共役系を伸ばすことができる。 The terpyridyl group-containing compound is preferably a compound having an aromatic ring in the molecule. Having an aromatic ring increases the molecular rigidity of the terpyridyl group-containing compound. In addition, the conjugated system can be extended.
上記テルピリジル基含有化合物の具体例としては、例えば以下のような化合物が挙げられる。
［式（１）中、Ｘは炭素原子又はケイ素原子を示し、Ｙは単結合、或いは、下記一般式（２）又は（３）で表される基を示す。］
Specific examples of the terpyridyl group-containing compound include the following compounds.
[In the formula (1), X represents a carbon atom or a silicon atom, and Y represents a single bond or a group represented by the following general formula (2) or (3). ]
［式（２）中、Ｒ１は水素原子、メチル基、エチル基又はフェニル基を示し、Ｒ２及びＲ３はそれぞれ独立に水素原子、メチル基又はエチル基を示し、ｎは１又は２を示す。］
[In the formula (2), R 1 represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, R 2 and R 3 each independently represent a hydrogen atom, a methyl group or an ethyl group, and n represents 1 or 2 Show. ]
［式（３）中、Ｒ４は水素原子、メチル基又はエチル基を示し、ｍは１〜３の整数を示す。］
[In formula (3), R 4 represents a hydrogen atom, a methyl group or an ethyl group, m is an integer of 1-3. ]
上記一般式（１）において、Ｙは上記一般式（２）又は（３）で表される基であることが好ましい。また、上記一般式（２）において、ｎは１又は２を示すが、１であることが特に好ましい。更に、上記一般式（３）において、ｍは１〜３の整数を示すが、１又は２であることが特に好ましい。上記一般式（１）において、Ｙが上記一般式（２）又は（３）で表される基である場合、ｎ又はｍの値を調整することで、分子サイズを調整することができる。 In the general formula (1), Y is preferably a group represented by the general formula (2) or (3). Moreover, in the said General formula (2), although n shows 1 or 2, it is especially preferable that it is 1. Furthermore, in the said General formula (3), m shows the integer of 1-3, but it is especially preferable that it is 1 or 2. In the general formula (1), when Y is a group represented by the general formula (2) or (3), the molecular size can be adjusted by adjusting the value of n or m.
本発明のテルピリジル基含有化合物は、カップリング反応により合成される化合物であることが好ましい。カップリング反応によりテルピリジル基含有化合物を合成することで、中心原子に結合する４つの有機基を簡便に同一のものとすることができる。 The terpyridyl group-containing compound of the present invention is preferably a compound synthesized by a coupling reaction. By synthesizing a terpyridyl group-containing compound by a coupling reaction, the four organic groups bonded to the central atom can be easily made the same.
テルピリジル基含有化合物は、例えば、炭素原子又はケイ素原子を中心原子として含む化合物と、テルピリジル基を含む化合物とをカップリングすることにより合成することができる。カップリング反応としては、反応操作が簡便であり、目的のテルピリジル基含有化合物が得られやすいことから、触媒にパラジウム化合物を用いる鈴木カップリング反応が好ましい。 The terpyridyl group-containing compound can be synthesized, for example, by coupling a compound containing a carbon atom or a silicon atom as a central atom with a compound containing a terpyridyl group. As the coupling reaction, a Suzuki coupling reaction using a palladium compound as a catalyst is preferable because the reaction operation is simple and the target terpyridyl group-containing compound is easily obtained.
鈴木カップリング反応により合成を行う場合、例えば、上記一般式（１）で表されるテルピリジル基含有化合物は、下記一般式（１−ａ）で表される化合物と、下記一般式（１−ｂ）で表される化合物とをカップリングすることにより合成することができる。 When the synthesis is performed by the Suzuki coupling reaction, for example, the terpyridyl group-containing compound represented by the general formula (1) includes the compound represented by the following general formula (1-a) and the following general formula (1-b). ) Can be synthesized by coupling with a compound represented by
上記一般式（１−ａ）において、Ｘ及びＹは一般式（１）中のＸ及びＹと同義であり、Ｚはハロゲン原子を示す。 In the said General formula (1-a), X and Y are synonymous with X and Y in General formula (1), Z shows a halogen atom.
カップリング反応は、公知の方法で行うことができ、例えば、原料化合物を触媒等の存在下、溶媒中で加熱還流することによって行うことができる。溶媒としては、トルエン、テトラヒドロフラン（ＴＨＦ）、ベンゼン等と、水とからなる二層系溶媒を用いることが好ましい。 The coupling reaction can be performed by a known method, for example, by heating and refluxing the raw material compound in a solvent in the presence of a catalyst or the like. As the solvent, it is preferable to use a two-layer solvent composed of toluene, tetrahydrofuran (THF), benzene and the like and water.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
［実施例１］
（炭素型テルピリジル基含有化合物の合成）
2,6-Di(pyridin-2-yl)pyridin-4-yl-4-boronicacidを文献（Michael,S. Bice, H. Prasenjit, M. Org. Lett., 2008, 10(12), 2513）に従って、Tetrakis[4-(iodo)phenyl]methaneを文献（Isabelle, A. et. al.,J. Am. Chem. Soc. 2001, 123, 8177）に従って、それぞれ合成した。2,6-Di(pyridin-2-yl)pyridin-4-yl-4-boronic acidを１．４５ｇ（５．２９ｍｍｏｌ）と、Tetrakis[4-(iodo)phenyl]methaneを０．７７ｇ（０．９３ｍｍｏｌ）とを、Ｐｄ（ＰＰｈ３）４触媒（２２０ｍｇ、０．１９ｍｍｏｌ）、炭酸ナトリウム（２．９６ｇ、２７．９ｍｍｏｌ、関東化学社製、特級）及びトリフェニルホスフィン（１．２２ｇ、４．６５ｍｍｏｌ、関東化学社製、特級）の存在下、窒素バブリングしたトルエン（１５０ｍＬ、関東化学社製）、水（１００ｍＬ）及びＴＨＦ（１００ｍＬ、関東化学社製、特級、蒸留後使用）の二層系溶媒で３３日間加熱還流を行った（鈴木カップリング）。反応後、析出した固体を濾別し、脱水クロロホルム（関東化学社製、特級）で洗浄して、目的物である下記式（４）で表される炭素型テルピリジル基含有化合物を得た（７１６ｍｇ、収率６１％）。
[Example 1]
(Synthesis of carbon-type terpyridyl group-containing compounds)
2,6-Di (pyridin-2-yl) pyridin-4-yl-4-boronicacid (Michael, S. Bice, H. Prasenjit, M. Org. Lett., 2008, 10 (12), 2513) Thus, Tetrakis [4- (iodo) phenyl] methane was synthesized according to the literature (Isabelle, A. et. Al., J. Am. Chem. Soc. 2001, 123, 8177). 1.45 g (5.29 mmol) of 2,6-Di (pyridin-2-yl) pyridin-4-yl-4-boronic acid and 0.77 g (0. 0. of Tetrakis [4- (iodo) phenyl] methane). 93 mmol), Pd (PPh 3 ) 4 catalyst (220 mg, 0.19 mmol), sodium carbonate (2.96 g, 27.9 mmol, manufactured by Kanto Chemical Co., Ltd., special grade) and triphenylphosphine (1.22 g, 4.65 mmol) In the presence of Kanto Chemical Co., Ltd., special grade), nitrogen-bubbled toluene (150 mL, Kanto Chemical Co., Ltd.), water (100 mL) and THF (100 mL, Kanto Chemical Co., Ltd., special grade, used after distillation) And refluxed for 33 days (Suzuki coupling). After the reaction, the precipitated solid was filtered off and washed with dehydrated chloroform (manufactured by Kanto Chemical Co., Ltd., special grade) to obtain a carbon-type terpyridyl group-containing compound represented by the following formula (4) as a target product (716 mg). Yield 61%).
（炭素型テルピリジル基含有化合物の分析１）
得られた炭素型テルピリジル基含有化合物について、プロトンＮＭＲ分析を行った。プロトンＮＭＲスペクトルを図１に示した。プロトンＮＭＲスペクトルから、上記式（４）で表される目的の化合物と１Ｈの数が一致し、また８．６〜８．８ｐｐｍ付近に３Ｈ、７．８ｐｐｍ及び７．４ｐｐｍ付近に１Ｈずつあり、これはテルピリジンに共通するピークであるため、目的物の合成が確認された。
(Analysis of carbon-type terpyridyl group-containing compound 1)
The obtained carbon-type terpyridyl group-containing compound was subjected to proton NMR analysis. The proton NMR spectrum is shown in FIG. From the proton NMR spectrum, the target compound represented by the above formula (4) matches the number of 1H, and 3H, 7.8 ppm, and 7.4 ppm are present near 8.6 to 8.8 ppm, respectively. Since this is a peak common to terpyridine, synthesis of the target product was confirmed.
（炭素型テルピリジル基含有化合物の分析２）
得られた炭素型テルピリジル基含有化合物について、ＭＡＬＤＩ−ＭＳ分析を行った。ＭＡＬＤＩ−ＭＳスペクトルを図２に示した。上記式（４）で表される目的物の分子量は１２４４．５であり、その存在がＭＡＬＤＩ−ＭＳスペクトルで確認された。
物性値：1H NMR (400 MHz, CDCl3)δ8.76 (1H, s), 8.72 (1H, d, J = 3.9Hz), 8.67 (1H,d, J = 8.1Hz), 7.88 (1H, dd, J = 1.7, 5.9Hz), 7.84 (1H, d, J = 8.1Hz), 7.48(1H,d, J = 8.5Hz), 7.32-7.37(1H, m); MALDI-TOF-MS 1245.1 (M+)
(Analysis of carbon-type terpyridyl group-containing compound 2)
The obtained carbon-type terpyridyl group-containing compound was subjected to MALDI-MS analysis. The MALDI-MS spectrum is shown in FIG. The molecular weight of the target compound represented by the above formula (4) was 1244.5, and its presence was confirmed by a MALDI-MS spectrum.
Physical properties: 1 H NMR (400 MHz, CDCl 3 ) δ8.76 (1H, s), 8.72 (1H, d, J = 3.9Hz), 8.67 (1H, d, J = 8.1Hz), 7.88 (1H, dd, J = 1.7, 5.9Hz), 7.84 (1H, d, J = 8.1Hz), 7.48 (1H, d, J = 8.5Hz), 7.32-7.37 (1H, m); MALDI-TOF-MS 1245.1 ( M + )
［実施例２］
（ケイ素型テルピリジル基含有化合物の合成）
2,6-Di(pyridin-2-yl)pyridin-4-yl-4-boronicacidを文献（Michael,S. Bice, H. Prasenjit, M. Org. Lett., 2008, 10(12), 2513）に従って、Tetrakis[4-(iodo)phenyl]silaneを文献（J.H.Fournier.; X.Wang.;J.D.Wuest. Can. J. Chem, 2003,81, 376-380）に従って、それぞれ合成した。2,6-Di(pyridin-2-yl)pyridin-4-yl-4-boronic acidを３２９ｍｇ（１．２ｍｍｏｌ）と、Tetrakis[4-(iodo)phenyl]silaneを３３１ｍｇ（０．４ｍｍｏｌ）とを、Ｐｄ（ＰＰｈ３）４触媒（４６．３ｍｇ、０．０４ｍｍｏｌ）、炭酸ナトリウム（６３７ｍｇ、６ｍｍｏｌ、関東化学社製、特級）及びトリフェニルホスフィン（２６２ｍｇ、１ｍｍｏｌ、関東化学社製、特級）の存在下、窒素バブリングしたトルエン（３０ｍＬ、関東化学社製）、水（２０ｍＬ）及びＴＨＦ（２０ｍＬ、関東化学社製、特級、蒸留後使用）の二層系溶媒で７日間窒素下にて加熱還流を行った。反応後、反応物の有機層を塩化メチレンで抽出し、カラム及びＨＰＬＣによる精製を行ったところ、目的物である下記式（５）で表されるケイ素型テルピリジル基含有化合物を得た（１２ｍｇ、０．０１ｍｍｏｌ、収率５％）。
[Example 2]
(Synthesis of silicon-type terpyridyl group-containing compounds)
2,6-Di (pyridin-2-yl) pyridin-4-yl-4-boronicacid (Michael, S. Bice, H. Prasenjit, M. Org. Lett., 2008, 10 (12), 2513) According to the literature, Tetrakis [4- (iodo) phenyl] silane was synthesized according to the literature (JHFournier .; X. Wang .; JDWuest. Can. J. Chem, 2003, 81, 376-380). 329 mg (1.2 mmol) of 2,6-Di (pyridin-2-yl) pyridin-4-yl-4-boronic acid and 331 mg (0.4 mmol) of Tetrakis [4- (iodo) phenyl] silane , Pd (PPh 3 ) 4 catalyst (46.3 mg, 0.04 mmol), sodium carbonate (637 mg, 6 mmol, manufactured by Kanto Chemical Co., special grade) and triphenylphosphine (262 mg, 1 mmol, manufactured by Kanto Chemical Co., special grade) Under reflux with heating under nitrogen for 7 days in a two-layer solvent of nitrogen bubbled toluene (30 mL, manufactured by Kanto Chemical Co., Inc.), water (20 mL) and THF (20 mL, manufactured by Kanto Chemical Co., Ltd., special grade, used after distillation). went. After the reaction, the organic layer of the reaction product was extracted with methylene chloride and purified by column and HPLC. As a result, a silicon-type terpyridyl group-containing compound represented by the following formula (5) was obtained (12 mg, 0.01 mmol, yield 5%).
（ケイ素型テルピリジル基含有化合物の分析１）
得られたケイ素型テルピリジル基含有化合物について、プロトンＮＭＲ分析を行った。プロトンＮＭＲスペクトルを図３に示した。プロトンＮＭＲスペクトルから、上記式（５）で表される目的の化合物と１Ｈの数が一致し、また８．４〜８．８ｐｐｍ付近に３Ｈ、７．８ｐｐｍ及び７．３ｐｐｍ付近に１Ｈずつあり、これはテルピリジンに共通するピークであるため、目的物の合成が確認された。
(Analysis of silicon-type terpyridyl group-containing compound 1)
The obtained silicon-type terpyridyl group-containing compound was subjected to proton NMR analysis. The proton NMR spectrum is shown in FIG. From the proton NMR spectrum, the target compound represented by the above formula (5) matches the number of 1H, and 3H, 7.8 ppm, and 1H each near 8.4 to 8.8 ppm. Since this is a peak common to terpyridine, synthesis of the target product was confirmed.
（ケイ素型テルピリジル基含有化合物の分析２）
得られたケイ素型テルピリジル基含有化合物について、ＭＡＬＤＩ−ＭＳ分析を行った。ＭＡＬＤＩ−ＭＳスペクトルを図４に示した。上記式（５）で表される目的物の分子量は１２６０であり、その存在がＭＡＬＤＩ−ＭＳスペクトルで確認された。
(Analysis of silicon-type terpyridyl group-containing compound 2)
The obtained silicon-type terpyridyl group-containing compound was subjected to MALDI-MS analysis. The MALDI-MS spectrum is shown in FIG. The molecular weight of the target product represented by the above formula (5) was 1260, and its presence was confirmed by a MALDI-MS spectrum.
Claims (4)
［式（１）中、Ｘは炭素原子又はケイ素原子を示し、Ｙは単結合、或いは、下記一般式（２）又は（３）で表される基を示す。］
［式（２）中、Ｒ１は水素原子、メチル基、エチル基又はフェニル基を示し、Ｒ２及びＲ３はそれぞれ独立に水素原子、メチル基又はエチル基を示し、ｎは１又は２を示す。］
［式（３）中、Ｒ４は水素原子、メチル基又はエチル基を示し、ｍは１〜３の整数を示す。］ The terpyridyl group-containing compound according to claim 1 or 2, wherein the terpyridyl group-containing compound is a compound represented by the following general formula (1).
[In the formula (1), X represents a carbon atom or a silicon atom, and Y represents a single bond or a group represented by the following general formula (2) or (3). ]
[In the formula (2), R 1 represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, R 2 and R 3 each independently represent a hydrogen atom, a methyl group or an ethyl group, and n represents 1 or 2 Show. ]
[In formula (3), R 4 represents a hydrogen atom, a methyl group or an ethyl group, m is an integer of 1-3. ]
The terpyridyl group-containing compound according to any one of claims 1 to 3, wherein the terpyridyl group-containing compound is a compound synthesized by a coupling reaction.
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| WO2016068478A3 (en) * | 2014-10-30 | 2016-08-04 | 주식회사 엘지화학 | Cyclic compound and organic light-emitting element comprising same |
| US10287398B2 (en) | 2014-12-30 | 2019-05-14 | Momentive Performance Materials Inc. | Siloxane coordination polymers |
| US10294332B2 (en) | 2014-12-30 | 2019-05-21 | Momentive Performance Materials Inc. | Functionalized siloxane materials |
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| JP2013014481A (en) * | 2011-07-05 | 2013-01-24 | Nissan Motor Co Ltd | Carbon material, metal loading carbon material using the same, and method for producing the metal loading carbon material |
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