Tetra-CMPO-derivatives of calix[4]arenes fixed in the 1,3-alternate conformation

Calix[4]arene derivatives fixed in the 1,3-alternate conformation and substituted at one side by four carbamoylmethylphosphine oxide (CMPO) residues were synthesised. Two CMPO groups are directly attached to the wide rim, while the second pair is bound to the narrow rim via a tri- or tetramethylene spacer. Similar compounds, in which two CMPO groups at the wide rim are combined with two picolinamide groups or two ionisable carboxylic groups at the narrow rim, were also prepared. Some of these calixarene derivatives were studied as extractants for lanthanides (La3+, Eu3+, Yb3+) and thorium (Th4+) from acidic solution into methylene chloride. For selected samples, stability constants in methanol were determined by spectrophotometric titrations. Three compounds (1b′, 13, 17) in the 1,3-alternate conformation and one intermediate in the cone conformation (18) were confirmed by a crystal structure.

[1]  Anthony L. Spek,et al.  Structure validation in chemical crystallography , 2009, Acta crystallographica. Section D, Biological crystallography.

[2]  Z. Kolarik.  Complexation and separation of lanthanides(III) and actinides(III) by heterocyclic N-donors in solutions. , 2008, Chemical reviews.

[3]  Nolan E. Dean,et al.  Affinity of the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) for large metal ions of higher charge. A crystallographic and thermodynamic study of PDA complexes of thorium(IV) and the uranyl(VI) ion. , 2008, Inorganic chemistry.

[4]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[5]  A. van Dorsselaer,et al.  Lanthanide complexation with CMPO and CMPO-calix[4]arenes in solution: spectrophotometric and electrospray mass spectrometric approaches. , 2007, Talanta.

[6]  D. Reinhoudt,et al.  Multicoordinate ligands for actinide/lanthanide separations. , 2007, Chemical Society reviews.

[7]  V. Böhmer,et al.  1,3-Alternate calix[4]arenes, selectively functionalized by amino groups. , 2005, Organic & biomolecular chemistry.

[8]  F. Sansone,et al.  Calixarene‐Based Picolinamide Extractants for Selective An/Ln Separation from Radioactive Waste , 2005 .

[9]  L. Delmau,et al.  Synthesis and Extraction Behaviour of Calix[4]arenes Partially Substituted at the Wide Rim by Carbamoylmethylphosphine Oxide (CMPO) Functions , 2003 .

[10]  V. Böhmer,et al.  Redetermination of 5,11,17,23-tetra-tert-butyl-25,27-di­(ethoxy­carbonyl­methoxy)-26,28-di­hydroxy­calix­[4]­arene chloro­form disolvate at low temperature , 2003 .

[11]  M. Baaden,et al.  Theoretical Studies on Lanthanide Cation Extraction by Picolinamides: Ligand–Cation Interactions and Interfacial Behavior , 2003 .

[12]  J. B. Christensen.  A Simple Method for Synthesis of Active Esters of Isonicotinic and Picolinic Acids , 2001, Molecules : A Journal of Synthetic Chemistry and Natural Product Chemistry.

[13]  Stefano Fontana,et al.  Thermodynamic and structural properties of Gd(III) complexes with polyamino-polycarboxylic ligands: basic compounds for the development of MRI contrast agents , 2000 .

[14]  Arduini,et al.  Rigidified calixarenes bearing four carbamoylmethylphosphineoxide or carbamoylmethylphosphoryl functions at the wide rim , 2000, Chemistry.

[15]  V. Huber,et al.  Synthesis of 3-Hydroxy-2-pyridinone Derivatives of 4-tert-Butylcalix[4]arenes: A New Class of Selective Extractants of Actinide(IV) Ions , 1999 .

[16]  S. E. Matthews,et al.  Conformationally Mobile Wide Rim Carbamoylmethylphosphine Oxide (CMPO)-Calixarenes. , 1999 .

[17]  D. Reinhoudt,et al.  Conformationally flexible calix[4]arene chromoionophores: optical transduction of soft metal ion complexation by cation-pi interactions , 1999 .

[18]  S. E. Matthews,et al.  Calix[4]arenes with CMPO functions at the narrow rim. Synthesis and extraction properties , 1999 .

[19]  T. Burke,et al.  Pentafluorophenyl ester activation for the preparation of N,N′-diaroylhydrazines , 1997 .

[20]  D. Reinhoudt,et al.  Synthesis of 1,2-bridged calix[4]arene-biscrowns in the 1,2-alternate conformation , 1997 .

[21]  C. Grüttner,et al.  LONG-CHAIN ALKYL ETHERS OF P-NITRO AND P-AMINOCALIXARENES , 1996 .

[22]  C. Grüttner,et al.  Calixarenes with diphenylphosphoryl acetamide functions at the upper rim. A new class of highly efficient extractants for lanthanides and actinides , 1996 .

[23]  M. Hudson,et al.  Recent advances in the treatment of nuclear wastes by the use of diamide and picolinamide extractants , 1995 .

[24]  D. Reinhoudt,et al.  Synthesis, Complexation, and Membrane Transport Studies of 1,3-Alternate Calix[4]arene-crown-6 Conformers: A New Class of Cesium Selective Ionophores , 1995 .

[25]  R. Blessing,et al.  An empirical correction for absorption anisotropy. , 1995, Acta crystallographica. Section A, Foundations of crystallography.

[26]  S. Harris,et al.  Selective Alkali and Alkaline Earth Cation Complexation by Calixarene Amides , 1992 .

[27]  S. Harris,et al.  Synthesis, x-ray crystal structures, and cation-binding properties of alkyl calixaryl esters and ketones, a new family of macrocyclic molecular receptors , 1989 .

[28]  R. Ungaro,et al.  The preparation and properties of a new lipophilic sodium selective ether ester ligand derived from p-t-butylcalix[4]arene , 1986 .

[29]  H. Gampp,et al.  Calculation of equilibrium constants from multiwavelength spectroscopic data--II: SPECFIT: two user-friendly programs in basic and standard FORTRAN 77. , 1985, Talanta.

[30]  George F. Vandegrift,et al.  THE TRUEX PROCESS - A PROCESS FOR THE EXTRACTION OF THE TKANSURANIC ELEMENTS EROM NITRIC AC In WASTES UTILIZING MODIFIED PUREX SOLVENT* , 1985 .

[31]  R. Ungaro,et al.  p-t-Butyl-calix[4]arene tetracarboxylic acid. A water soluble calixarene in a cone structure , 1984 .