Study On Synthesis And Properties Of Macrocycles Containing Glycoluril Units

Cucurbituril (CB), as a type of novel synthetic acceptor, has attracted considerable attentions of chemists. Studies in the field of their molecular recognition, supramolecular catalysis and molecular assembly have been widely carried out. In this thesis, cucurbit[n]uril (CB[n]), cucurbituril derivatives and their analogues were prepared; molecular recognition properties of CB[n] for diazonium salts and alkyldiammonium ions were investigated by ¹H NMR spectroscopy and UV-vis spectrophotometric titration; the potential utilization of CB[n] and their derivatives in the separation science were investigated.1. The recent research progress of cucurbituril including synthesis of cucurbituril and their derivatives, their molecular recognition, supramolecular catalysis, molecular assembly was reviewed.2. The synthesis and separation CB[n] have been studied, and the preparation of CB's derivatives has been attempted. CB[n] mixture could be synthesized by the condensation of glycoluril and formaldehyde in concentrated HCl, and then they could be separated and purified one by one according to their different solubility in the same solvent (HCl solution or methanol aqueous solution). The products were determined by elemental analysis, ¹H NMR, ¹³C NMR and FAB-MS (or ESI-MS). By merization condensation reaction of substituted glycoluril and unsubstituted glycoluril with formaldehyde, we attempted to synthesize CB's derivatives. The products have been analyzed by FAB-MS.3. Molecular recognition and rotaxane assembly based on CB[n] were explored by NMR spectroscopy, UV-vis spectrophotometric titration and X-ray single crystal diffraction analysis.(1) The first supramolecular adduct (H₃O)₂[Cu(H₂O)₄](SO₄)₂·2(C₃₀H₃₀N₂₀O₁₀)·24(H₂O) based on CB[5] was synthesized and characterized by single crystal X-ray diffraction analysis;(2) Inclusion interaction between CB[n] and several aminoadamantane derivatives was studied by ¹H NMR. The results showed CB[7] could form 1:1 inclusion complexes with these guests, but other CB[n] could not include the guests efficiently;(3) For the first time, inclusion complexation between CB[n] (n = 5,6,7,8) and three diazonuim salts with different sizes in variable acid solution was investigated by 'H NMR spectroscopy and UV-vis spectrophotometric titration. It was found that the complex stability is dominated by the size/shape-matching between host and guest. And the concentration of the acid also influenced binding constants notablely;(4) The interactions between CB[n] (n=5, 6, 7, 8) and 1,6-hexanediamine, spermine in acidic aqueous solution were investigated by using NMR technique. *H NMR spectroscopic analysis indicated that in addition to CB[6], CB[7] also can form a stable inclusion complexes with two guests. CB[5] cannot form pseudorotaxane with 1,6-hexanediamine, this was confirmed by the crystal structure of the complex. The cavity of CB[8] seems to be large for binding 1,6-hexanediamine efficiently;(5) On the base of above results, new rotaxanes was constructed thought the self-assembly of pseudorotaxanes of cucurbit[n]uril (n = 6,7)/l, 6-hexanediamine and sodium tetraphenylborate. The obtained rotaxanes are held intact solely by noncovalent interactions, and are characterized by elemental analysis, 'H NMR, ESI-MS.4. For the first time, CB[7] was employed as an additive in capillary electrophoresis. The effects of CB[7] concentration, different organic solvent component (acetonitrile or methanol) and content on the EOF behavior were investigated. CB[7] was fully protonated under the experimental conditions used. Dynamic adsorption of protonated CB[7] onto the capillary wall caused the reversal of the EOF. The electrophoretic separations of six nitrobenzenes and three type of the isomers can be accomplished with a buffer containing CB[7]. Furthermore, a probable separation mechanism in the presence of CB[7] was also proposed.5. Perhydroxylcucurbit[6]uril was for the first time grafted to silica gel as a new stationary phase. The binding reaction has been by IR spectra mensuration. IR measurements were undertaken to confirm the immobilization reaction works. The results indicated that the stationary phase behaves as a hydrophilic-interaction chromatographic packing. Finally, six alkaloids were separated on the stationary phase.6. A novel kind of [2+2] azamacrocyclic compounds has been synthesized by a one-step condensation of diethylenetriamine (or triethylenetetramine) with formaldehydeand rigid diphenylglycoluril in methanol. The compounds have been characterized by H NMR, I3C NMR and ESI-MS; crystal structure of the compound 14b was determined by single-crystal X-ray diffraction; the structure properties of the compound 15 have been further investigated by NMR technique (DEPT, 'H-'H COSY, gHMBC). Preliminary Ni2+ binding studies were undertaken using electrospray ionisation mass spectrometry (ESI-MS). The results showed these macrocycles might be a kind of binuclear acceptors.