Synthesis and crystal structures of lower rim amine and carbamoyl substituted calixarenes as transfer agents for oxyanions between an aqueous and a chloroform phase

Nicholas J. Wolf, Emil M. Georgiev, Alexander T. Yordanov, Bruce R. Whittlesey, H. Fred Koch, D. Max Roundhill

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Abstract

The calixarene amides 5,11,17,23-tert-butyl-25,27-(carbamoylmethoxy) calix[4]arene 1, 5,11,17,23-tert-butyl-25,27-(N,N-diethyl-2-carbamoylmethoxy) calix[4]arene 3, 5,11,17,23-tert-butyl-25,27-methoxy-26,28-(N,N-diethyl-2-carbamoylethoxy) calix[4]arene.sodium triiodide 5, 5,11,17,23-tert-butyl-25,27-propoxy-26-(N,N-diethyl-2-carbamoylmethoxy) calix[4]arene 6, 5,11,17,23-tert-butyl-25,26,27,28-(carbamoylmethoxy) calix[4]arene 9, 5,11,17,23-tert-butyl-25,26,27,28-(N,N-diethyl-2-carbamoylmethoxy) calix[4]arene.sodium iodide 11 and 5,11,17,23,29,35-tert-butyl-37,38,39,40,41,42-(carbamoylmethoxy) calix[6]arene 13 have been prepared by reacting the precursor calixarene with either 2-bromoacetamide or 2-chloro-N,N-diethylacetamide. The structures of 5 and 11 have been verified by X-ray crystallography. The crystals of 5, C58H74I3N2NaO6, are monoclinic, P21/c, and those of 11, C71H112IN4NaO11, are triclinic P1̄. The calixarene amines 5,11,17,23-tert-butyl-25,27-(2-aminoethoxy) calix[4]arene 2, 5,11,17,23-tert-butyl-25,27-(N,N-diethyl-2-aminoethoxy) calix[4]arene 4, 5,11,17,23-tert-butyl-25,27-propoxy-26-(N,N-diethyl 2-aminoethoxy) calix[4]arene 7, 5,11,17,23-tert-butyl-25,27-methoxy-26-(N,N-diethyl 2-aminoethoxy) cal[4]arene 8, 5,11,17,23-tert-butyl-25,26,27,28-(2-aminoethoxy) calix[4]arene hydrochloride 10, 5,11,17,23-tert-butyl-25,26,27,28-(N,N-diethyl-2-aminoethoxy) calix[4]arene hydrochloride 12 and 5,11,17,23,29,35-tert-butyl-37,38,39,40,41,42-(2-aminoethoxy) calix[6]arene 15 have been synthesized by the borane reduction of either the precursor amide or cyanomethoxy derivative. The structure of 10 has been verified by X-ray crystallography. The crystals of 10, C56H94Cl2N4O10, are triclinic, P1̄. The calix[4]arenes 2, 3, 4, 6, 10, 11 and 12 have been investigated as extractants for the anions HPO42-, SeO42-, VO3-, ReO4-, CrO42-, WO42- and MoO42- from water into a chloroform layer. Measurement of the remaining metal content in the aqueous layer by ICP has been used to obtain the distribution coefficient and percentage extraction into chloroform from solutions having a pH of both 0.85 and 7.0. These data generally show that the calix[4]arene amines are better extractants than the calix[4]arene amides, and that the former are usually better extractants from acidic solutions.

Original languageEnglish
Pages (from-to)885-896
Number of pages12
JournalPolyhedron
Volume18
Issue number6
DOIs
StatePublished - Jan 22 1999

Keywords

  • Amidocalixarenes
  • Aminocalixarenes
  • Oxyanions
  • Phase transfer

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