Synthesis And Derivatization Of Monohydroxy Citrulline

Cucurbit[n]urils?Q[n]s?are a kind of macrocyclic host compounds in supramolecular chemistry,which has a rigid opening cavity and polar potrals rimmed with carbonyl groups.The chemistry based on cucurbit[n]urils has become an impoetant research area in macrocyclic chemistry and supramolecular chemistry.However,the poor solubility and chemical inertness of cucurbit[n]urils have become the main limitation for their applications.Therefore,the synthesis of chemical activied cucurbit[n]urils has become an important branch in cucurbit[n]uril chemistry.Since Kim and co-workers firstly synthesized the perhydroxycucurbit[n]urils?n =5-8?in 2003,it has opened the way for the synthesis of chemical activied cucurbit[n]urils.Compared to perhydroxycucurbit[n]urils,monohydroxycucurbit[n]urilshas the advantage of controllable functionalization.The worksin this thesis are based on amoderate oxidation method reported by Ouari and Bardelang in 2015,that isusing the UV photolysis of hydrogen peroxide?H₂O₂?as a source of hydroxyl radicals to introduce limited hydroxyl groups to outer surface of cucurbit[n]urils.The main contents of this thesis are as follows:?1?synthesis,separation and characterization of monohydroxycucurbit[6] uril and monohydroxycucurbit[7]uril;?2?optimizing the reaction conditions of this synthetic method and improving the yield of monohydroxycucurbit[n]uril;?3?synthesis and characterization of a propargyl-O-Q[7]using a monohydroxycucurbit[7]uril;?4?synthesis of some azide-based fluorescence probe,includingderivatives of quinoline,coumarin,vinyl dipyridine and dansyl chloride;?5?grafting the azide-based fluorescence probe molecule on to the propargyl-O-Q[n]s by click reaction and examination of the obtained supramolecular probe for certain compounds recognizing;?6?synthesis of an N-methyl-4-methyl-pyridinyl-substituted calix[4]arene and its azidation,and investigationof itssupramolecular assemblies with the cucurbit[n]urils,and their responding properties.The experimental results revealed that: 1)the yield of monohydroxy substituted reaction can be increased by reducing the amount of oxidant and increasing the irradiation time;2)based on the principle of Williamson reaction,combined with the use of microwave reactor,the yield of propargylcucurbit[7]uril can be improved;3)the product of azidation ofpropargyl-O-Q[7] shows anunconspicuous recognition ofmetalcation;4)the functionalized calix[4]arene showed no obviously interaction with HMe Q[6] and HMe Q[7]in both DMSO and water by variation of fluorescence emission,however,it showed a strong interaction with Q[8] in water by intense fluorecence emission with a red shift,and the formed assemblyshowed recognition for certain compounds,auch asadamantanamine hydrochloride by significant change of fluorecence emission.