Layered Zirconium Phosphonate-phosphates With Chirality: Synthesis, Characterization And Basic Properties

There is still a great impetus to design and synthesize chiral solidmaterials for enantioseparation and asymmetric heterogeneous catalysis.One promising strategy for obtaining these materials is to incorporate chiralorganic moieties in the open and robust frameworks with void space, suchas large cavities and interlayer spacing. It is important to select appropriateorganic ligands, meanwhile, to explore a controlled route of synthesis isgreat significance to realize rational design. Zeolite-like zirconium phosphonates can be considered as a versatileclass of layered materials in which many designs can be realized under mildcondition, by an appropriate choice of the organic group. The high rigidityof the lamellae of γ-zirconium phosphate (Zr(PO4)(H2PO4)·2H2O) allow oneto prepare stable hybrid materials by topotactic exchange ofdihydrogenphosphates with mono- or diphosphonic acids. Although thezirconium atoms of inorganic matrix have very weak capability as activesites to organic reaction,many desired metal ions can be easily exchangedinto the frameworks. The property of intercalation of them had been appliedin entanioseparation resolution. Proline is the only natural amino acid which contains an importantfive-membered ring as part of a secondary amino group. Proline and itsderivatives or analogs, as very important chiral sources, have been widelyapplied in stereoselective synthesis,entanioseparationand biochemistry. - 143 -手性层状膦酸-磷酸锆的合成,表征及基本性能研究 正文 吉林大学博士学位论文 In this thesis, chiral N-phosphonomethyl-L-proline (H3PMP),N-phosphono- methyl-1,3-thiazolidine-4-carbonyl acid (H3PMTA) aresynthesized in high yield from commerical amino acids. Two mix-typelayeded zirconium phosphonates formulated as Zr(PO4)0.6(HPO4)0.1(HPMP)1.1(HF)0.55·1.0H2O (mix-ZrPMP) and Zr(PO4)0.6(HPO4)0.10(HPMT)1.1(HF)0.55·2.0H2O (mix-ZrPMT) are obtained by reaction of H3PMP andH3PMTA with ZrOCl2·8H2O in the presence of HF, respectively areobtained under mild conditions. Of both phosphonates, CO2H and CO2 -groups coexist. Of mix-ZrPMP, easy intercalation-deintercalation, two-sidedion-exchange capability, robustness and high crystallinity implicate that theymight be utilized over a wide field. In particular, the optical activity of allorganic moieties is remained under the experimental condition. High cystallinity of γ-ZrP is obtained by our motified method based onliterature. With γ-type structure, two compounds formulated as Zr(PO4)(H2PO4)0.53(H2PMP)0.47·2.0H2O(γ-ZrPMP) and Zr(PO4)(H2PO4)0.50(H2PMT)0.50·1.6H2O (γ-ZrPMT) are obtained by topotactic reaction of H3PMP and H3PMTAwith γ-ZrP in the presence of water-acetone, respectively. The host materialspossess the properties of intercalation- deintercalation and optical activity. New chiral phosphonic acids and zirconium phosphonates might havepotential applications in asymmetric synthesis, enantioseparation andbiochemistry.