Molecular Recognition Study Based on a Multi-point Interaction Utilizing Metal Complexes

基于金属配合物多点相互作用的分子识别研究

• 批准号: 04640550
• 负责人: UMETANI Shigeo
• 金额: $ 1.09万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640550/
• 关键词: Multi-point interaction; Hydrogen bond; Association Reaction; Acylpyrazolone; Aminoalcohol; NMR; Thermodynamics; Molecular Recognition; 金属錯体; ピリジルカルビノール; ヒドロキシピリジン

Some 4-acyl-5-pyrazolones have been synthesized and the association reaction between their copper or zinc chelates and neutral ligands with one or two functional groups has been investigated spectrophotometrically. The binding constants in chloroform for neutral ligands such as aminoalcohols, hydroxypyridines and pyridylcarbinols which have both nitrogen and hydroxy group were measured.The binding constants depend on the acidity of acylpyrazolones, the basicity of nitrogen atom and the steric effect. Concurrently, the ligands having a hydroxy group were found to show larger binding constants, indicating the hydrogen bonding between the hydroxy group and the donating oxygens of acylpyrazolones. It was evidently shown that the strength of this hydrogen bond depends on the number of the methylene group between the nitrogen atom and the hydroxy group and the electron withdrawing substituent at the 4-position of acylpyrazolones.The values of DELTAH and DELTAS for amines and pyridines with a hydroxy group in the reaction with copper acylpyrazolonates were more negative as compared to those for with no hydroxy group. It was corifirmed that the ^1H-NMR signal of the methylene protons adjacent to the hydroxy group shifted to the high field in the reaction of a bifunctional ligand and zinc acylpyrazolohate. This high field shift indicates that the methylene protons come on close to 4-benzoyl or 4-naphthoyl group of acylpyrazolones on forming the hydrogen bond. The two point interaction between metal acylpyrazolonates and the bifunctional ligands could be confirmed by the thermodynamic study and ^1H-NMR spectra.

合成了4-酰基-5-吡唑啉酮类化合物，并研究了它们的铜、锌螯合物与带有一个或两个官能团的中性配体之间的缔合反应。在氯仿中测定了氨基醇、羟基吡啶和吡啶基甲醇等含氮和羟基的中性配体与酰基吡唑啉酮的结合常数，结合常数与酰基吡唑啉酮的酸度、氮原子的碱性和空间位阻效应有关。同时，发现具有羟基的配体显示出较大的结合常数，表明羟基与酰基吡唑啉酮的供氧基团之间存在氢键。结果表明，这种氢键的强度取决于氮原子与羟基之间的亚甲基数目和4-位吸电子取代基的数目，有羟基的胺和吡啶与酰基吡唑啉铜反应的Δ H和Δ TAS值比无羟基的大.证实了在双官能团配体与酰基吡唑锌反应中，羟基邻位亚甲基质子的~ 1H-NMR信号向高场移动。这种高场位移表明，亚甲基质子靠近酰基吡唑啉酮的4-苯甲酰基或4-萘甲酰基形成氢键。通过热力学研究和核磁共振氢谱证实了酰基吡唑啉酮金属配合物与双官能团配体之间存在两点相互作用。

项目成果

Q.T.H.Le: "Liquid-Liquid Extraction of Lanthanides with a Highly Acidic Extractant, 3-Phenyl-4-benzoy-5-isoxazolone, in the Presence or Absence of Tri-n-octylphosphine Oxide" Anal.Chim.Acta. 272. 293-299 (1993)

Q.T.H.Le：“在存在或不存在三正辛基氧化膦的情况下，使用高酸性萃取剂 3-苯基-4-苯甲酰基-5-异恶唑酮对镧系元素进行液-液萃取”Anal.Chim.Acta。

S.Umetani: "Improved Separation in the Solvent Extraction of Lanthanides by β-Diketones through a Controlled Separation of the Two Donating Oxygens." J.Chem.Soc.,Chem.Commun.78-79 (1993)

S.Umetani：“通过控制两种供体氧的分离来改进 β-二酮溶剂萃取镧系元素的分离。J.Chem.Soc.，Chem.Commun.78-79 (1993)

S.Umetani: "Improvement of Separation in the Solvent Extraction of Alkaline Earths by the Use of 18-Crown-6 as a Masking Reagent." J.Chem.Soc.,Chem.Commun.914-916 (1993)

S.Umetani：“使用 18-Crown-6 作为掩蔽试剂改进碱土溶剂萃取中的分离。”

S.Umetani: "Improvement of Separation in the Solvent Extraction of Alkaline Earths by the Use of 18-Crown-6 as a Masking Reagent" J.C.S., Chem.Commun.914-916 (1993)

S.Umetani：“使用 18-Crown-6 作为掩蔽试剂改善碱土溶剂萃取中的分离”J.C.S.，Chem.Commun.914-916 (1993)

K.Ogura: "Voltammetric Study on the Transfer of Alkali and Alkaline Earth Metals at the Aqueous/Organic Interface Facilitated by Phosphine Oxides." Bull.Chem.Soc.Japan. 66. 1971-1978 (1993)

K.Ogura：“氧化膦促进碱金属和碱土金属在水/有机界面转移的伏安研究”。