1,3-Alternate calix[4]arenecrown-5 conformers: new synthetic ionophores with better K+/Na+ selectivity than valinomycin

Alessandro Casnati, Andrea Pochini, Rocco Ungaro, Carlo Bocchi, Franco Ugozzoli, Richard J.M. Egberink, Helma Struijk, R.J.W. Lugtenberg, Feike de Jong, David Reinhoudt

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    Abstract

    New 25,27-dialkoxycalix-[4]arenecrown-5 conformers 8, 10, and 11 have been synthesized and studied. The compounds 8a and 8b, fixed in 1,3-alternate structure, have been obtained in 57 and 40% yield, respectively, by reaction of the corresponding 25,27-dialkoxycalix[4]arenes 7a-b with tetraethylene glycol di-p-toluenesulfonate in the presence of Cs2CO3. The cone 10a and 10b and the partial cone 11 conformers were obtained by selective demethylation of the 25,27-dimethoxycalix[4]arenecrown-5 (6a) and subsequent dialkylation with NaH/DMF and KOtBu/THF, respectively. In the solid state (X-ray), compound 6a adopts a flattened cone conformation, which is also found to be most abundant in CD3CN and CD3OD solution. Upon complexation with potassium picrate compound 6a was converted quantitatively into the 1,3-alternate conformation. All new ligands synthesized were used in the extraction of alkali metal cations from H2O into CHCl3, and as active components in supported liquid membranes and in chemically modified field effect transistors. Results were compared to those obtained with with the natural antibiotic valinomycin 1. All ligands showed high selectivity for potassium. Ligand 8a, fixed in the 1,3-alternate conformation, is more selective than valinomycin and shows the highest K+/Na+ selectivity known so far.
    Original languageUndefined
    Pages (from-to)436-445
    JournalChemistry: a European journal
    Volume2
    Issue number2
    DOIs
    Publication statusPublished - 1996

    Keywords

    • METIS-105886
    • IR-10885

    Cite this

    Casnati, Alessandro ; Pochini, Andrea ; Ungaro, Rocco ; Bocchi, Carlo ; Ugozzoli, Franco ; Egberink, Richard J.M. ; Struijk, Helma ; Lugtenberg, R.J.W. ; de Jong, Feike ; Reinhoudt, David. / 1,3-Alternate calix[4]arenecrown-5 conformers: new synthetic ionophores with better K+/Na+ selectivity than valinomycin. In: Chemistry: a European journal. 1996 ; Vol. 2, No. 2. pp. 436-445.
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    title = "1,3-Alternate calix[4]arenecrown-5 conformers: new synthetic ionophores with better K+/Na+ selectivity than valinomycin",
    abstract = "New 25,27-dialkoxycalix-[4]arenecrown-5 conformers 8, 10, and 11 have been synthesized and studied. The compounds 8a and 8b, fixed in 1,3-alternate structure, have been obtained in 57 and 40{\%} yield, respectively, by reaction of the corresponding 25,27-dialkoxycalix[4]arenes 7a-b with tetraethylene glycol di-p-toluenesulfonate in the presence of Cs2CO3. The cone 10a and 10b and the partial cone 11 conformers were obtained by selective demethylation of the 25,27-dimethoxycalix[4]arenecrown-5 (6a) and subsequent dialkylation with NaH/DMF and KOtBu/THF, respectively. In the solid state (X-ray), compound 6a adopts a flattened cone conformation, which is also found to be most abundant in CD3CN and CD3OD solution. Upon complexation with potassium picrate compound 6a was converted quantitatively into the 1,3-alternate conformation. All new ligands synthesized were used in the extraction of alkali metal cations from H2O into CHCl3, and as active components in supported liquid membranes and in chemically modified field effect transistors. Results were compared to those obtained with with the natural antibiotic valinomycin 1. All ligands showed high selectivity for potassium. Ligand 8a, fixed in the 1,3-alternate conformation, is more selective than valinomycin and shows the highest K+/Na+ selectivity known so far.",
    keywords = "METIS-105886, IR-10885",
    author = "Alessandro Casnati and Andrea Pochini and Rocco Ungaro and Carlo Bocchi and Franco Ugozzoli and Egberink, {Richard J.M.} and Helma Struijk and R.J.W. Lugtenberg and {de Jong}, Feike and David Reinhoudt",
    year = "1996",
    doi = "10.1002/chem.19960020413",
    language = "Undefined",
    volume = "2",
    pages = "436--445",
    journal = "Chemistry: a European journal",
    issn = "0947-6539",
    publisher = "Wiley-VCH Verlag",
    number = "2",

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    1,3-Alternate calix[4]arenecrown-5 conformers: new synthetic ionophores with better K+/Na+ selectivity than valinomycin. / Casnati, Alessandro; Pochini, Andrea; Ungaro, Rocco; Bocchi, Carlo; Ugozzoli, Franco; Egberink, Richard J.M.; Struijk, Helma; Lugtenberg, R.J.W.; de Jong, Feike; Reinhoudt, David.

    In: Chemistry: a European journal, Vol. 2, No. 2, 1996, p. 436-445.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - 1,3-Alternate calix[4]arenecrown-5 conformers: new synthetic ionophores with better K+/Na+ selectivity than valinomycin

    AU - Casnati, Alessandro

    AU - Pochini, Andrea

    AU - Ungaro, Rocco

    AU - Bocchi, Carlo

    AU - Ugozzoli, Franco

    AU - Egberink, Richard J.M.

    AU - Struijk, Helma

    AU - Lugtenberg, R.J.W.

    AU - de Jong, Feike

    AU - Reinhoudt, David

    PY - 1996

    Y1 - 1996

    N2 - New 25,27-dialkoxycalix-[4]arenecrown-5 conformers 8, 10, and 11 have been synthesized and studied. The compounds 8a and 8b, fixed in 1,3-alternate structure, have been obtained in 57 and 40% yield, respectively, by reaction of the corresponding 25,27-dialkoxycalix[4]arenes 7a-b with tetraethylene glycol di-p-toluenesulfonate in the presence of Cs2CO3. The cone 10a and 10b and the partial cone 11 conformers were obtained by selective demethylation of the 25,27-dimethoxycalix[4]arenecrown-5 (6a) and subsequent dialkylation with NaH/DMF and KOtBu/THF, respectively. In the solid state (X-ray), compound 6a adopts a flattened cone conformation, which is also found to be most abundant in CD3CN and CD3OD solution. Upon complexation with potassium picrate compound 6a was converted quantitatively into the 1,3-alternate conformation. All new ligands synthesized were used in the extraction of alkali metal cations from H2O into CHCl3, and as active components in supported liquid membranes and in chemically modified field effect transistors. Results were compared to those obtained with with the natural antibiotic valinomycin 1. All ligands showed high selectivity for potassium. Ligand 8a, fixed in the 1,3-alternate conformation, is more selective than valinomycin and shows the highest K+/Na+ selectivity known so far.

    AB - New 25,27-dialkoxycalix-[4]arenecrown-5 conformers 8, 10, and 11 have been synthesized and studied. The compounds 8a and 8b, fixed in 1,3-alternate structure, have been obtained in 57 and 40% yield, respectively, by reaction of the corresponding 25,27-dialkoxycalix[4]arenes 7a-b with tetraethylene glycol di-p-toluenesulfonate in the presence of Cs2CO3. The cone 10a and 10b and the partial cone 11 conformers were obtained by selective demethylation of the 25,27-dimethoxycalix[4]arenecrown-5 (6a) and subsequent dialkylation with NaH/DMF and KOtBu/THF, respectively. In the solid state (X-ray), compound 6a adopts a flattened cone conformation, which is also found to be most abundant in CD3CN and CD3OD solution. Upon complexation with potassium picrate compound 6a was converted quantitatively into the 1,3-alternate conformation. All new ligands synthesized were used in the extraction of alkali metal cations from H2O into CHCl3, and as active components in supported liquid membranes and in chemically modified field effect transistors. Results were compared to those obtained with with the natural antibiotic valinomycin 1. All ligands showed high selectivity for potassium. Ligand 8a, fixed in the 1,3-alternate conformation, is more selective than valinomycin and shows the highest K+/Na+ selectivity known so far.

    KW - METIS-105886

    KW - IR-10885

    U2 - 10.1002/chem.19960020413

    DO - 10.1002/chem.19960020413

    M3 - Article

    VL - 2

    SP - 436

    EP - 445

    JO - Chemistry: a European journal

    JF - Chemistry: a European journal

    SN - 0947-6539

    IS - 2

    ER -