Synthesis And Ion Recognition Properties Of Benzo-15-Crown-5 Sulfonylhydrazide Derivatives

1. A simple introduction was made to the crown ether compounds and its complexation behavior which included the general coordination characteristics (solublity, UV-vis spectram characteristics, as well as the extraction properties) and the factors (the effects of ligands, ions and solvent) which impacted the stability and selectivity of the crown ether complexes. Since the concept of the"supermolecular"have been put forward, molecular recognition become one of a hot point of the supermolecular chemistry. Due to the important role of crown ether compounds in molecular recognition, the last part of this chapter shows the new development and application of crown ether compounds in molecular recognition including cationic recognition, recognition of neutral molecules, the anion identification and the synergistic identification of anion and cation.2. A new series of crowned sulfonylhydrazide derivatives 2a²c have been synthesized by replacement of phenylhydrazine with 4′-sulfonyl chloride benzo-15-crown-5 (1) and characterized by IR, ¹H NMR, ¹³C NMR and elemental analysis. Compound 1 was synthesized starting from sulphonation of benzo-15-crown-5 with oil of vitriol to get (benzo-15-crown-5)-4′-sulfonyl acid, then neutralized with CaCO₃ and Na₂CO₃ to give its sodium salt, the latter reacted with SOCl₂ to yield (benzo-15-crown-5)-4′-sulfonyl chloride. The UV-vis datas indicated that the compounds can recognize Cu²⁺ and Fe³⁺ and form 1:1 stoichiometry complexes,which also indicated that these receptors could act as selective colorimetric sensors for basic anions F^-, CH₃COO^- and H₂PO₄^- over other anions, such as Cl^-, Br^-, I^-, HSO₄^-, and ClO₄^-, in DMSO. And the number of nitro groups can affect the activity and selectivity of the receptors. ¹H NMR experiments of the receptor 2c with F^- revealed that the recognition mechanism of anions is deprotonation/protonation of the NH fragments, which was responsible for the dramatic color change.3. A new series of crown ether sulfonyldihydrazide derivatives 6a⁶n have been synthesized by replacement of aromatic hydrazides with 4′-sulfonyl chloride benzo-15-crown-5 (1) and characterized by IR, ¹H NMR, ¹³C NMR and elemental analysis. The UV-vis datas indicated that the receptors 6d and 6n exhibited selective recognition of F^- and CH₃COO^- over other anions, such as Cl^-, Br^-, I^-, HSO₄^-, H₂PO₄^- and ClO₄^-, in DMSO.4. A series of p-toluene sulfonylamido acetacylhydrazone derivatives were synthesized from p-toluenesulfonyl chloride which reacted with glycine to get the intermediate p-toluene sulfonylamido glycine, then through the esterification, hydrazinolysis to afford another intermediate p-toluene sulfonylamido acethydrazide, which condensed with different aldehydes to obtain the target compounds that were characterized by IR, ¹H NMR, ¹³C NMR spectra and elemental analysis. The DFT-B3LYP methods with 6-31G* basis set have been applied to the advanced reaction energy, the charges distribution and the linear orbital level of the title compounds 4a～4g. The plant growth regulating activity tests showed that part of the compounds had good activity as plant growth regulator.