Synthesis, Characterization And Activity Of Saccharide-metal And Organotin Complexes

This dissertation were divided into three parts; the first one is the synthesis of rare earth coordinating with saccharide derivatives, the second is the synthesis of saccharide-transition metal complexes and its activity on hydrolysis of PNPP, the third is the synthesis of organotin complexes and its antitumour activity.First, we synthesized two series of sacchride-rare earth complexes and studied their activity on hydrolysis of DNA. We found the compound (5) had good antitumour activity, so we use it and its analogue compound (6) as ligands, react with LaCl₃, NdCl₃, SmCl₃, GdCl₃, DyCl₃, YbCl₃ respectively. Then two series of coordination complexes of rare earth ions were synthesized. The saccharide-rare earth complexes were characterized by elementary analysis, FT-IR, UV spectra and molar conductance and we also speculated the possible structure of the complexes. The two series of complexes have similar structure: Ln:L=1 :4, four coordination oxygen atoms are from carboxyl, four coordination oxygen atoms from acylamide, and the other is from H₂O, the coordination number is nine.We synthesis three series of sacchride-trasition metal complexes and studied their activity on hydrolysis of PNPP. We replaced the oxygen atom of the sugar by nitrogen atom, synthesized the stronger binding carbohydrate ligands. They are N, N'-(1- amino-1-deoxy-β-D-glucose)propane diamine, N, N'-(1-amino-1-deoxy-β-D-maltose) propane diamine, N, N", N"-(1-amino-1-deoxy-β-D-galactose)-triaminotriethyl amine. The ligands reacting with CuCl₂ and NiCl₂ gained six complexes. They were all characterized by elementary analysis. FT-IR. UV spectra and molar conductance and we also speculated the possible structure of the complexes. We studied the catalytic activities of glycosylamine-metal complexes on hydrolysis of picolinate. and found that hydrolysis is significantly accelerated in the presence ofcomplexes over spontaneous hydrolysis. In low pH the Cu(ll) complexes have higher activity, but it is lower when pH is higher. While the Ni(ll) complexes is on the contrary. We also find that when the OH group of the sugar coordination with the metal the hydrolysis activity is higher. So we can decide that the OH group of the sugar play important role in the hydrolysis.Dibutyltin( IV) oxide complex reacts with the cantharidin analogue. 4'-(7-oxabicyclo[2,2,l]-5-heptane-2,3-dicarboximide) benzoic acid and a-(7-oxabicyclo[2,2,l]-5-heptane-2,3-dicarboximide) acetic acid to give the complexes [(p-C8H8NO3-C6H4-COOBu2Sn)2O]2(29), (p-C8H8NO3-C6H4-COO)2SnBu2 (30) and (a-C8H8NO3-CH2-COO)2SnBu2 (31) which have been characterized by IR, 'H NMR, 13C NMR and 119Sn NMR. Single x-ray crystal structure analysis has been determined for the compound 29, which was analogue to most other [(RCOOBu2Sn)2O]2. The dimer features central of Bu4Sn2O2 unit with the two Bu2Sn groups being linked via bridging oxygen atom. Each tin atom adopts distorted trigonal bipyramides via two carbons from a dibutyl moiety and three oxygen atoms from cantharidin analogue and bridging oxygen. In vitro test shows compound 29-31 exhibit high cytotoxicity against P388 and HL-60, but it is lower against A-549. The effects of compounds 29-31 have been tested on human hematopoietic progenitors using clonogenic effect. Cytotoxic concentration and no effect dose concentration have been determined after scoring colonies derived from hematopoietic progenitors incubated 14 days. Results show that compound 29 is less myelotoxic than compound 30 and 31 according cytotoxic and no effect doses.