6402-09-1Relevant articles and documents
4-Phosphoryl Pyrazolones for Highly Selective Lithium Separation from Alkali Metal Ions
Du, Hao,Hennersdorf, Felix,Lindoy, Leonard F.,Schaper, Gerrit,Steup, Johannes,Weigand, Jan J.,Wenzel, Marco,Zhang, Jianfeng,Zheng, Shili
supporting information, (2021/11/10)
Effective receptors for the separation of Li+ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4-phosphoryl pyrazolones, HL2-HL4, in the presence of the typical industrial organophosphorus co-ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li+ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co-ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid-liquid extraction in the presence of TOPO revealed an unprecedented high Li+ extraction efficiency (78 %) for HL4 compared to the use of the industrially employed acylpyrazolone HL1 (15 %) and benzoyl-1,1,1-trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li+ over Na+, K+ and Cs+ under mild conditions (pH ～8.2) confirms that HL2-HL4 represent a new class of ligands that are very effective extractants for use in lithium separation.
Catalytic System-Controlled Divergent Reaction Strategies for the Construction of Diversified Spiropyrazolone Skeletons from Pyrazolidinones and Diazopyrazolones
Fang, Feifei,Han, Xu,Hu, Shulei,Li, Chunpu,Liu, Hong,Wang, Qian,Wang, Run,Zhou, Yu
supporting information, p. 21327 - 21333 (2021/08/20)
A catalytic system-controlled divergent reaction strategy was here reported to construct four types of intriguing spiroheterocyclic skeletons from simple and readily available starting materials via a precise chemical bond activation/[n+1] annulation cascade. The tetraazaspiroheterocyclic and trizazspiroheterocyclic scaffolds could be independently constructed by a selective N?N bond activation/[n+1] annulation cascade, a C(sp2)-H activation/[4+1] annulation and a novel tandem C(sp2)-H/C(sp3)?H bond activation/[4+1] annulation strategy, along with a broad scope of substrates, moderate to excellent yields and valuable transformations. More importantly, in these transformations, we are the first time to capture a N?N bond activation and a C(sp3)?H bond activation of pyrazolidinones under different catalytic system.
Tuned structure and DNA binding properties of metal complexes based on a new 4-acylpyrazolone derivative
Xi, Wei,Song, Fu-Qiang,Xia, Xue-Li,Song, Xue-Qin
, p. 2281 - 2290 (2020/02/20)
It is common knowledge that the spatial structure of substrates is the major influencing factor in DNA binding. To tune the binding affinity of DNA, a new 4-acylpyrazolone derivative ligand, (2-hydroxy-N′-((5-hydroxy-3-methyl-1-(4-nitrophenyl)-4,5-dihydro-1H-pyrazol-4-yl)(phenyl)methylene)benzohydrazide) (H2L) and its three complexes have been prepared and well characterized. Reaction of H2L with CuCl2 resulted in a mononuclear compound with tetra-coordinated quadrilateral plane, [Cu(HL)Cl] (1). When H2L was coordinated to Cu(OAc)2, a dinuclear Cu(ii) compound with chemical formula of [Cu2L2(CH3OH)2]·CH3OH (2) was obtained, and the coordination geometry of Cu(ii) is a square pyramid. Upon assembly of H2L with Mn(OAc)2, a quite different dinuclear compound with chemical composition of [Mn2L2(O CH3)2(H2O)2]·CH3OH (3) was afforded, where Mn(iii) displayed distorted octahedral configurations. DNA binding studies were performed on H2L and its three complexes by means of electron absorption titration and EB-DNA competition experiments, and the results indicate they all bind DNA in an intercalation mode, and their binding affinity follows the order of 1 > 2 > 3 > H2L. In addition, time-dependent density functional theory (TD-DFT) calculations were performed for H2L and its three complexes to better clarify the electronic transitions in the UV-vis spectra.
