TY - JOUR
T1 - Synthesis and crystal structures of lower rim amine and carbamoyl substituted calixarenes as transfer agents for oxyanions between an aqueous and a chloroform phase
AU - Wolf, Nicholas J.
AU - Georgiev, Emil M.
AU - Yordanov, Alexander T.
AU - Whittlesey, Bruce R.
AU - Fred Koch, H.
AU - Roundhill, D. Max
N1 - Funding Information:
We thank the U.S. Army Research Office, the U.S. Department of Energy through the Pacific Northwest Laboratory, and NATO for support of this research. Supplementary Material Available
PY - 1999/1/22
Y1 - 1999/1/22
N2 - 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.
AB - 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.
KW - Amidocalixarenes
KW - Aminocalixarenes
KW - Oxyanions
KW - Phase transfer
UR - http://www.scopus.com/inward/record.url?scp=0003322853&partnerID=8YFLogxK
U2 - 10.1016/S0277-5387(98)00375-1
DO - 10.1016/S0277-5387(98)00375-1
M3 - Article
AN - SCOPUS:0003322853
VL - 18
SP - 885
EP - 896
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 6
ER -