115646-53-2Relevant academic research and scientific papers
Lower rim calix(4)arene ketone derivatives and their interaction with alkali metal cations. Structural and thermodynamic (solution and complexation) characterisation of the tetraphenyl ketone derivative and its sodium complex
Danil de Namor,Kowalska,Castellano,Piro,Sueros Velarde,Villanueva Salas
, p. 4010 - 4021 (2001)
A modified method for the synthesis of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra(benzoyl)methoxycalix(4)arene (1) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra(acetoyl)methoxycalix(4)arene (2) using 18-crown-6 as phase transfer catalyst is reporte
Synthesis, X-ray Crystal Structures, and Cation-Binding Properties of Alkyl Calixaryl Esters and Ketones, a New Family of Macrocyclic Molecular Receptors
Arnaud-Neu, Francoise,Collins, Elizabeth M.,Deasy, Mary,Ferguson, George,Harris, Stephen J.,at al.
, p. 8681 - 8691 (1989)
Calixarenes (N=4,6,8) have been converted into polyfunctional esters and ketones in a search for new macrocycles capable of showing ionophoric activity.Treatment with alkyl bromoacetates furnished the calixaryl acetate series, whereas chloroacetone-potassium iodide, phenacyl chloride, 1-adamantyl bromomethyl ketone, and bromopinacolone were used to make the calixaryl ketones series.The crystal structures of ethyl calixaryl acetate (7), methyl calixaryl acetate (13), ethyl calixaryl acetate (11), and calixaryl methyl ketone (20) have been determined.Thecrystals of 7 are triclinic, space group P, with two molecules in the unit cell of dimensions a = 12.434(2) Angstroem, b = 15.033(3) Angstroem, c = 17.286(4) Angstroem, α = 103.01(2) deg, β = 102.97(1) deg and γ = 94.68(1) deg.The crystals of 13 are monoclinic, space group C2/c, with eight molecules in the unit cell of dimensions a = 27.066(6) Angstroem, b = 21.392(6) Angstroem, c = 21.348(7) Angstroem, and β = 119.32(2) deg.The crystals of 11 are monoclinic, space group C2/c, with four molecules in the unit cell of dimensions a = 21.906(4) Angstroem, b = 11.805(2) Angstroem, c = 23.534(4) Angstroem, and β = 91.79(2) deg.The crystals of 20 are orthorhombic, space group Pbcn, with four molecules in the unit cell of dimensions a = 19.644(7) Angstroem, b = 12.712(3) Angstroem, and c = 22.115(7) Angstroem.Both 11 and 20 have crystallographically imposed 2-fold molecular axes.The analysis establishes that all three tetramer derivatives possess the cone conformation in the solid state where the pendant-functionalized side chains are mutually syn with respect to the calixarene substructure and are thus preorganized for ionreception.NMR measurements confirm the existence of the cone conformation for these tetramers in solution at room temperature.In contrast, the centrosymmetric hexamer ester 11 has three adjacent groups syn, but the inversion symmetry places the other three ester groups in the anti position on the opposite side of the macrocycle.Extraction studies with alkali metal picrates from aqueous solution into dichloromethane, transport studies with alkali metal thiocyanates through a dichloromethane membrane, and stability constant measurements with alkali metal salts by UV absorption spectroscopy in methanol and acetonitrile were used to assess the ionophoric activity of these calixarene derivatives.The tetramer esters and ketones display peak selectivity for the sodium ion, the tetraketones being generally more efficient binders than the tetraesters.The hexaester extracts K(1+) better than Na(1+) and displays a plateau selectivity after K(1+).The octamers are the least effective ionophores.The selectivities shown by the picrate extraction technique are broadly mirrored in the transport studies.Stability constants range from 2 to 6, ...
