Synthesis Of Calix[4]arene Sulfur-bearing Derivatives

Calixarenes,which are basket-shaped macrocyclic compounds of potential interest for host-guest complexation studies,represent the new type of receptor after cyclodextrins and crown ethers.Due to their easy functionalization and strong complexing properties towards cations, anions and neutral molecules,they have received particular interests of numerous chemists in recent years.Functional calixarenes have been applied successfully to biomimetic research and separation science and technology.In this paper,The novel calix[4]arene derivatives which branch chain includes sulfydryl and nitryl group was designed and synthesized,we also offer an improved synthetic route to this compound from p-tert-butylcalix[4]arene(1),p-tert-butylcalix[4]arene(1)is readily accessible synthesized by reaction of p-tert-butl-phenol and formaldehyde.The removal of the p-butyl groups from(1)has been shown to proceed smoothly to afford calix[4]arene(2),and this compound would appear to be perfectly adapted to functionalization in the aryl ring at the positions para to the hydroxyl groups,ethyl bromoacetate is added in the presence of acetonitrile reacts with calix[4]arene yields 25,26,27,28-(ethylacetatoethoxy)-calix[4]arene.25,26,27,28-(ethylacetatoethoxy)-calix[4]arene(3) was easily deoxidezed by LiHAl₄,the product is 25,26,27,28-hydroxyethoxy-calix[4]arene(4). Then PBr3 is added to solution of compound(4)to take the place of hydroxyl groups at 0℃..We get the compound(5)- 25,26,27,28-(2-bromoethoxy)-calix[4]arene.Compound(5)and kalium thioacetate was dissolved in acetonitrile,and 25,26,27,28-thioacetatoethoxy-calix[4]arene(6)is prepared as a dark brown solid.Hydrolyzing(6)and and nitrify it,the target molecular is got.