Synthesis And Hosts-guest Complexation Of Pillararene-based Polycyclic Compounds

Pillar[n]arenes,a novel class of host molecules,have shown excellent host-guest binding properties with different guests including neutral molecules and anion-cation guests such as halohydrocarbon,alkanes and pyridinium salts.Since the pillar[n]arenes were firstly reported by Japanese scientists Ogoshi et al in 2008,their derivatives have attracted more attention because of their applications in host-guest recognition chemistry,self-assemble chemistry,biomaterials chemistry and fluorescence material chemistry.Calixarenes,the third generation supramolecular compounds,are a kind of macricyclic oligomers composed of multiple phenols linked by methylene groups.Due to its variable sizes of cavity,the conformation in varied forms and easy modification of functional groups,etc.,calixarenes were extensive and in-depth in molecular recognitions,drug deliverys,new materials,high-performance catalysts and other relevant fields.In view of the structural advantages and complementary for pillararene unit and calixarene unit,the calixarenes with different types and cavity sizes were grafted into the pillararene's skeleton.In this thesis,a series of novel polycyclic and multilocus pillararene derivatives were successfully synthesized and their host-guest properties were studied.(1)In this thesis,bromoalkylcopillar[5]arenes 2a?2d were successfully synthesized by 1,4-dimethoxy benzene,1-(bromo-alkoxy)-4-methoxybenzene and paraformaldehyde with Lewis acid FeCl3 as catalyst.t-Butyl calix[n=4,6,8]arenes were synthesized from p-t-butylphenol and formaldehyde under catalysis of base.And then,three types of eleven pillararene-based polycyclic compounds were prepared by Williamson reaction of bromoalkylcopillar[5]arenes,and they were pillar[5]arene-cali[4]xarenes 3a?3c,pillar[5]arene-cali[6]xarenes 4a?4d and pillar[5]arene-cali[8]xarenes 5a?5d which have not been reported in literature.The synthetic conditions of the target products were investigated preliminarily,and the novel compounds were characterized and analyzed by means of infrared spectroscopy,nuclear magnetic resonance,and mass spectrometry techniques.(2)In this thesis,N-methyl-l-naphthylmethylamine derivatives G1?G12 were successfully synthesized by using N-methyl-1-naphthylmethyl amine,dibromoalkanes or bromoalkanes as starting materials under catalysis of K2CO3,in which compounds G1?G4?G7 and G9?G12 have not been reported in literature.The twelve compounds were characterized and analyzed by means of infrared spectroscopy,nuclear magnetic resonance,and mass spectrometry techniques.(3)The host-guest complexation between pillar[5]arene derivatives 3a?5d and guests Gl?G12 were investigated in CDCl3 by 1H NMR.The results indicated that these target compounds can complex guests via excellent synergistic effects between the pillararene units and calixarene units.Meanwhile,the host-guest complexation properties were not weaken as the size of calixarene cavity increased.On the other hand,the complexation behaviour of G1?G3 was very similar to the guests G4?G6 in the host-guest system.But for the G7?G9 and G10?G12,their host-guest properties showed significantly difference.For the guests G7?G9,the single peak of methylene-CH2-connected to naphthalene ring was split into two set of single peaks with the integral ratio 1:1.In contrast,the peak(doublet)of methylene protons-CH2-in G10?G12 was split into two set of dd peaks after complexation and their integral ratio was closed to 1.The similar phenomenon was also observed for methyl(N-CH3)that their single peak showed seperating two new resonances.These results indicated that the designed hosts have potential application in chiral recognition for the two types of guests G7?G9 and G10?G12.