Chemistry And Bioactivity Of The Heterocyclic Compounds Containing Phosphorus And Oxygen

In recent years, heterocyclic compounds containing phosphorus have been paid attentions due to their applications in molecular recognition, supermolecular chemistry, chiral catalyst and life science. In this dissertation, eight-, eleven-, fourteen-, sixteen and twenty-four-membered heterocyclic compounds containing phosphorus and oxygen were studied and the results are showed as follow.1. Two reactions occurring in the process of synthesis of 12H-dibenzo[d,g][l,3,2]-dioxa phosphocin derivates were studied systematically.(1)The reaction of 6-chloro-2,4,8,10-tetrachIoro-12H-dibenzo [d,g][l,3,2] dioxaphosphocin-6-sulfide (2a) with n-PrOH in intoluene under refluxing in the present of triethylamine was proved to be hydrolysis process, and in the present of triethylamine, the esterification of 2a with only ethanol and n-propanol can go smoothly.(2) A new way to prepare phosphate diesters from thiophosphate ester and di-thiophosphate diester was discovered in the process of studying the reaction of 6-alkoxy-2,4,8,10- tetrachloro -12H-dibenzo[d,g] [l,3,2]-dioxa phosphocin-6-sulfide with DMSO, and the reaction mechanism can be described as two steps: hydrolysis and then oxidation.2. Three series of nine new12H-dibenzo[d,g][l,3,2]-dioxaphosphocin derivates(A,B,C) with good solubility were prepared. Their structures were confirmed by 31P NMR, 1H NMR, 13C NMR, elemental analysis, IR and MS.3. After preparing four new a,w-diols (D, E, F and G), novel eleven-, fourteen-, sixteen and twenty-four-membered heterocyclic thiophoshosphoryl chloride (H, J, O, S) were synthesized successfully by means of ring-closure reaction of D, E, F, G with PSC13, respectly, and a new fourteen-membered di-thiophosphate diester triethylamide salt L was synthesized also. Their structures were confirmed by X-ray diffraction analysis except 1H NMR, 13C NMR, elemental analysis, IR and MS.The X-ray diffraction analysis showed that fourteen-, sixteen- and twenty-four- members heterocycles are of almost symmetry unregulated cycles and eleven-membered heterocycle is of a highly asymmetry structure. Fourteen- and twenty-four-membered thiophosphoryl chloride form complex with chloroform at ratio of 1:1 but fourteen-membered di-thiophosphate diester triethylamide salt L at ratio of 1:2. The chloroform lies out of the cavity of mother molecular.4. Nineteen new eleven-, fourteen-, sixteen and twenty-four-membered thiophosphoryl amides (I1-6, K1-6, P1, T1-6)were prepared. Their structures were confirmed by 31P NMR, 1H NMR, 13C NMR, elemental analysis and IR, some of them by MS also.5. New compounds were tested as germicide and plant growth regulators, and results showed their low bioactivities. The relations between structure and bioactivity need investigating further.6. Preliminary studying on the complex performance of H, J, O, S and L with metal cations Li+, Na+, K+, Mg2+, Co2+ were carried out. The results showed that L forms complex with CoCl2 and twenty-four-membered may form super molecular compound with...