Study On The Synthesis, Characterization And Properties Of New Type Organophosphonic Acids And Heteropoly Compounds

Organophosphonic acid is the focus of research cross the fields of inorganic chemistry,organic chemistry,biochemistry,medicine,agricultural and catalysis et al. Organophosphonic acid has various kinds,one of them,β-amminoethylphosphonic acid plays a very important biochemical role in the mechanism of animals. There are many ways reported to prepare for β-amminoethylphosphonic acid and its analogues. However,most of the ways include at least two reactions and the operations are very troublesome,the purifying procedures are complex and their total yield are low. One of the work in the thesis is to synthesize eleven organophosphonic acids in simple and one procedure with high yield and high purification,in which seven organophosphonic acids were synthesized for the first time,and characterized by elemental analysis,IR spectra,31P NMR spectra. Heteropoly acid is a kind of cluster type compound of metallic oxide. In nearly thirty years,the research of heteropoly compound has made great progress in the catalyst,inorganic ions exchanger,analytic reagent,anti-virus or anti-cancer medicine,and functional material et al. People introduce organic or organic metallic groups into heteropoly compounds to embellish parts of the skeleton structure outside or inside the heteopoly anions,it is of active importance to change the structures and properties of heteropoly compounds and to develop new applied fields. There were the reports that the heteropoly compounds with organophosphonic or organoarsonic acids as coordinate center have been synthesized twenty years ago,but no organophosphono-heteropoly acids with the coordinate ratio above 1:8 have been reported yet,especially the coordinate centers of Keggin and Dawson structure phosphono-heteropoly acids with P:M=1:12 and 2:18 are still limited as inorganic phosphorus acid. In the thesis,it is tried to employ new type organophosphonic acids acquired in experiments to synthesize relevant organophosphono-heteropoly compounds with high coordinate ratios. If organophosphono-heteropoly compounds with high coordinate ratios can be synthesized,it will be a great breakthrough in the field of heteropoly acids,which is not only of great theoretical and academic significance,but also of expansive pratical prospect. In the thesis,seventeen Keggin and Dawson type heteropoly acids and theircharge-transfer complexes have been synthesized with the organophosphonic acids acquired in the experiment for the first time,and characterized by elemental analysis,ICP emission spectra,IR,UV spectra,XRD,TG-DSC thermal analysis and 31P NMR spectra,some of the heteropoly compounds have been characterized by polarmetric or cyclic voltammogram analysis. Their acidic strengths and numbers have been measured. And all the results have been compared with those of heteropoly acids PW12 (H3PW12 O40?nH2O) or P2W18 (H6P2W18O62?nH2O). In the thesis,we have synthesized several single crystals of heteropoly acids and the charge-transfer complexes of heteropoly acid. One single crystal of the charge-transfer complex of heteropoly acid 4b has been measured and its relevant data have been acquired. The data of the single crystal of 4b demonstrates that the heteropolyanions of 4b is Keggin type structure. But the result of the single crystal measurement has some factors which can't be confirmed. It is supposed temporarily that the P-C band is possible to be broken with the presence of heat and acid in the course of synthesizing this Keggin type heteropoly acid. It is needed to be further explored or confirmed by data of single crystals whether the organic side chain will be kept or the P-C band will be broken in the other heteropoly acids. The thesis has put forward four probable mechanisms of P-C band broken in dimethylaminoethylphosphonic acid under the condition of synthesizing heteropoly acid for the first time and compared the relative probability of the four possible mechanisms. It is inferred in the thesis that the most possible mechanism of the reaction is t...