Study On Synthesis And Extraction Of Ag+,Pb2+ By Calix[4]Arene Derivatives

Calixarenes have received increasing attention in recent years,not only because they possess recognition abilities toward ions and neutral little-molecules,but also because they are very useful building platforms to construct compounds with pre-organized structures.Calixarenes modified by heteroatom-containing groups have good complexation and recognization abilities toward transitional metal and heavy metal cations,thus could be widely used in various fields.In this thesis,the thiacalix[4]arene-crown derivatives were designed and synthesized,and calix[4]arene derivatives 6 was synthesized more easily compared with the old routine which was designed by my group.The recent development of calixarenes was introduced in chapter 1.A review of their methods of syntheses,structures,chemical modifications,properties and potential applications was outlined, especially the thiacalix[4]arene derivatives.In chapter2,the p-tert-butycalix[4]arenel was firstly reacted with aluminium trichloride to produce calix[4]arene derivative2 in the condition of toluene as solvent.Then the drivative2 was alkylated with 1,2-dibromoethane to give calix[4]arene drivative3 in the presence of potassium carbonate.The derivative4 was synthesized from the reaction of drivative3 with 1,3-dimercaptopr-opane in the presence of potassium hydroxide in the condition of toluene and dimethylformamide as mix-solvent.Next,the derivative5 was synthesized from the reaction of derivative4 with nitric acid in the presence of acetic acid under chloroform as solvent.Next,the derivative6,which currently was not reported,was Synthesized from the reaction of derivative5 with stannous chloride dehydrate under ethanol,acetone and chloroform as mix-sOlvent.Then the drivativel was alkylated with 1,2-dibr-omoethane to give calix[4]arene drivative7 in the presence of potassium carbonate.The derivative8 was synthesized from the reaction of drivative7 with 1,3-dimercaptopropane in the presence of potassium hydroxide in the condition of toluene and dimethylformamide as mix-solvent.The structures were confirmed by ¹H-NMR,IR,EA and M.p.In chapter 3,calixarene derivatives 4,6,8 were used as the extractant for the extraction of Ag⁺ and calixarene derivatives 4,8 were used as the extractant for the extraction of Pb²⁺.The influences of fundamental parameters affecting the extraction including extraction time,pH,concentration of extractant,initial concentration of ions have been studied.On the basis of the extraction experiment, the following conclusion could be made:calixarene derivatives 4,6,8 had excellent extraction ability for Ag⁺,each of their highest extraction efficiencies was 89.29%,90.10%,93.27%,and the highest extraction efficiencies of Pb²⁺ was 62.10%,65.10%by calix[4]arene derivatives4,8.The extraction ability for Ag⁺ was more excellent by using calixarene derivatives 4,8 than Pb²⁺ by using calixarene derivatives 4,8.It indicated that calixarene derivatives 4,8 had the selective ability for extraction Ag⁺ and Pb²⁺.According to the HSAB theory and compared the volume of crown with the volume of atom, the experimental phenomenon was briefly discussed.The anti-extraction of Ag⁺ and Pb²⁺ with strong acid terms was also investigated.In chapter 4,the full paper was concluded.The shortcomings as well as the prediction have been concerned.