Molecular Design of Calixarene,Part 4, Synthesis of Novel Double‐Armed p‐(tert‐Butyl)calix[4]arene‐Derived Amides and Their Lead(II)(Pb2+)‐Selective‐Electrode Properties

A series of novel double‐armed p‐(tert‐butyl)calix[4]arenes, carrying benzoylamido, 4‐nitrobenzoylamido, isonicotinamido, α‐naphthamido, acetamido, propionamido, or butyramido groups (see 2 – 8 , resp.) were synthesized in 80 – 86% yield by the reaction of the lower‐rim 1,3‐bis(aminoethoxy)‐substituted calix[4]arenediol 1 with the corresponding acylating agents. Their structures were established by elemental analysis, mass, IR, UV, and ¹H‐NMR spectroscopy. Ion‐selective electrodes (ISEs) for Pb²⁺, carrying 2 – 8 in a PVC membrane as neutral ionophore, were prepared, and their selectivity coefficients for Pb²⁺ (K) were determined against other heavy‐metal ions, alkali and alkaline earth metal ions, and ammonium ions by means of the separate‐solution method. The results obtained indicated that the electrodes based on the calix[4]arene‐derived amides 2 – 8 as the neutral ionophores were all Pb²⁺ selective and exhibited almost theoretical Nernstian slopes, except for 3 and 4 . Typically, the Pb²⁺‐selective electrode based on 6 – 8 exhibited almost Nernstian slopes for Pb²⁺ over a relatively wide concentration range and had a fast response time as well as a long lifetime, although the silver ion interfered strongly. These ISEs based on 6 – 8 showed a relatively good Pb²⁺ selectivity against most of the interfering cations examined, except for Ag⁺. The effect of the side‐arm functions of calix[4]arene derivatives 2 – 8 on the Nernstian slopes and on the selectivity coefficients for Pb²⁺ obtained with the Pb²⁺ ISEs based on 2 – 8 is discussed.