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

摘要

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 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, C_(58)H_(74)I_3NaO_6, are monoclinic, P2_1/c, and those of 11, C_(71)H_(112)IN_4NaO_(11), are triclinic P1. 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,-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, C_(56)H_(94)Cl_2N_4O_(10), are triclinic, P1. The calix[4]arenes 2,3,4,6,10,11 and 12 have been investigated as extractants for the anions HPO_4~(2-), SeO_4~(2-), VO_3~-, ReO_4~-. CrO_4~(2-), WO_4~(2-) and MoO_4~(2-) 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 that the calix[4]arene amides, and that the former are usually better extractants from acidic solutions.