1118-66-7Relevant articles and documents
Electrochemical behaviour of amino substituted β-amino α,β-unsaturated ketones: A computational chemistry and experimental study
Ngake, Tankiso Lawrence,Potgieter, Johannes Hermanus,Conradie, Jeanet
, p. 1070 - 1082 (2019)
The synthesis, identification and electrochemical properties are reported here, for a series of five novel and seven known amino substituted β-amino α,β-unsaturated ketones (bidentate N,O-ligands) of the type CH3COCHC(NHR)CH3, where R = H, Ph, CH2Ph, CH(CH3)2, p-CF3-Ph or p-tBu-Ph (Series 1), as well as type PhCOCHC(NHR)CH3, where R = H, Ph, p-NO2-Ph, 3,5-di-Cl-Ph, 2-CF3-4-Cl-Ph, and also PhCOCHC(NHPh)CF3 (Series 2). The cyclic voltammograms measured in CH3CN, generally exhibit both a chemically and electrochemically irreversible reduction peak between ?1.2 V and ?3.1 V vs FcH/FcH+, producing an unstable radical anion, for most of these 1,3-amino ketones. Only ligands PhCOCHC(NHPh)CH3, PhCOCHC(NHPh)CF3 and PhCOCHC(NH(p-NO2-Ph))CH3, showed reversible electrochemical behaviour, at higher scan rates. Density functional theory (DFT) calculations proved the unpaired spin density in the radical anion to be distributed over the pseudo-aromatic O–C–C–C–N backbone of the 1,3-amino ketones, extending further over the phenyl rings of the phenyl-containing ligands. Various DFT calculated energies, such as the energy of the lowest unoccupied molecular orbital (the orbital into which the electron is added upon reduction), as well as the DFT calculated gas phase adiabatic electron affinities, relate linearly to the experimentally measured reduction potential. These obtained linear relationships confirmed that good communication via conjugation exists, between the R substituent on the amino group and the rest of the 1,3-amino ketone.
Solid-state and Computational Study of “Venus fly-trap” Geometric Parameters for 1,5-Cyclooctadiene in PdII and PtII β-Enaminonato Complexes
Hill, Tania N.,Roodt, Andreas
, p. 763 - 774 (2018)
The cod ligand (cis,cis-1,5-cyclooctadiene) can be superficially considered to mimic similarities in spatial behavior of a leaf of the Venus fly-trap (Dionaea muscipula). Thus, the synthesis of an unsymmetrical bidentate trans ligand (N,O-donor atoms) based on the β-enaminonate backbone is introduced to evaluate the electronic and steric influence on the structural behavior of the cod ligand when coordinated to a square planar transition metal. A range of platinum(II) / palladium(II) complexes of the type [M(cod)(N,O-Bid)]A (M = PtII, PdII; β-enaminonato ligand (N,O-Bid) = NH-acac, NMe-acac, NPh-acac; A = BF4–, PF6–) is reported. The complexes were fully characterized, including by detailed X-ray structural investigations. Theoretical calculations on the [M(cod)(N,O-Bid)]+ complexes for the complete nickel triad are also described and the structural behavior of the cod ligand critically evaluated. The influence of the variation of the β-enaminonato ligands on the coordination arrangement of the cod was investigated and found that no significant changes to the M–C and C=C bond lengths were observed. The Venus fly-trap jaw angle (ψ), however, varies by ca. 8° and the twist angle (τ) by ca. 10°, whereas the cod bite angle (χ), as well as the β-enaminonato ligand bite angle (N–M–O; θ) both remain virtually constant. Calculated spectroscopic tendencies within the Ni-triad are also included.
An Improved Preparation of Enaminones from 1,3-Diketones and Ammonium Acetate or Amine Acetates
Baraldi, P. G.,Simoni, D.,Manfredini, S.
, p. 902 - 903 (1983)
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Metal-Free Cascade Annulation Approach for Modular Assembly of Alkynyl/Benzoyl Functionalized Quinolines
Tang, Qiang,Yuan, Meng,Duan, Jiahui,Xu, Keke,Li, Ruxue,Xie, Mengqing,Kong, Shuwen,He, Xinwei,Shang, Yongjia
supporting information, (2022/01/19)
A concise and efficient synthetic method for alkynyl quinolines through TfOH-promoted cascade 1,4-conjugate addition/intramolecular annulation/aromatization process is established. By virtue of reactive aza-o-AQM (in situ generated from modular propargylamine), this reaction proceeds smoothly to afford a variety of alkynyl quinolines in good to excellent yields. This transition-metal-free process features halogen groups tolerance, such as the ?Cl, ?Br, and ?I groups; thus, this protocol circumvents the inherent shortcomings of the existing Sonogashira coupling of halogenated quinolines.
β-Enaminones over recyclable nano-CoFe2O4: a highly efficient solvent-free green protocol
Eidi, Esmaiel,Kassaee, Mohamad Z.,Cummings, Peter T.
, p. 5787 - 5799 (2018/05/14)
Abstract: β-Enaminone and its derivatives have emerged among the finest bioactive intermediates. High yields of several β-enaminones (86–97%) are achieved through treatment of substituted aromatic and aliphatic amines with cyclic/acyclic 1,3-diketones, over the magnetically separable cobalt ferrite nanoparticles (CoFe2O4 NPs). The latter was prepared upon co-precipitation. Its purity, fine crystallinity, elemental distributions, morphology, magnetic features, and thermal stability were confirmed by Fourier transform infrared, X-ray diffraction, energy dispersive X-ray spectrometry, scanning electron microscopy, vibrating sample magnetometry, and thermal gravimetric analysis analyses. Thus, CoFe2O4 NPs acted as an excellent green heterogeneous nanocatalyst for synthesis of β-enaminones and gave good recyclability, while showing insignificant loss of their activity. Graphical Abstract: [Figure not available: see fulltext.].
