Studies On Synthesis, Characterization And Biological Activities Of Derivations Of 9-Hydroxy-Fluorene-9-Carboxylic Acid And Their Metal Complexes

In this thesis three ligands of derivatives of 9-hydroxy-9H-fluorene-9-carboxylic acid were synthesized with phenanthraquinone as material. They were ester 9-hydroxy-fluorene-9-carboxylate, 9-hydroxyl-9H-fluorene-9-carbohydrazide (L1), N'-acetyl-9-hydroxyl-9H-fluorene-9-carbohydrazide (L2). Twelve new complexes containing ligands of Mn(II),Fe(III),Co(II),Ni(II),Cu(II),Zn(II) were designed and synthesized by L1 and L2, and single crystals of ethyl 9-hydroxy-fluorene-9-carboxylate and [Co(C₁₆H₁₃N₂O₃)₂]·2CH₃OH were obtained.The chemical formulae and possible structures of the compounds were confirmed based on Elementary analysis, Conductance, IR, UV-vis, ¹HNMR, ¹³CNMR. 9-hydroxyl-9H-fluorene-9-carbohydrazide (L1) was coordinated to the metal ions by the mol. rate of 2:1 or 3:1, formed steady structure. N'-acetyl-9-hydroxyl-9H-fluorene-9-carbohydrazide (L2) was coordinated to the metal ions by the mol. rate of 2:1 or 3:1, formed complexes of structure of octahedron.The crystal structures of ethyl 9-hydroxy-fluorene-9-carboxylate and [Co(C₁₆H₁₃N₂ O₃)₂]·2CH₃OH were determined by X-ray diffraction. The crystal data are as follow:The crystal structure of ethyl 9-hydroxy-fluorene-9-carboxylate belong to triclinic crystal system and P-1 space group with a=11.2422(10) A, b=11.8831(10) A, c= 11.9561(10) A,β=63.2250(1)°, V=1328.4(2) A³, Z=4, Dc=1.271 g.cm^-3, F(000)=536,μ(Mo-Kα)=0.09 mm^-1, R₁=0.0520, wR₂=0.1240. Two independent molecules have the different orientation in an asymmetric unit. In each molecule, the thirteen carbon atoms in the fluorene are almost on the same plane, while the hydroxyl and the ethoxycarbonyl groups are located on the two sides of the fluorene plane respectively.The crystal structures of [Co(C₁₆H₁₃N₂O₃)₂]·2CH₃OH belong to monoclinic crystal system and P2(l)/n space group, with a=l3.1379(7) A, b=l 7.7809(10) A, c=14.7403(8) A,β=110.0580(10)°, V=3234.5(3) A³, Z=4, Dc=1.408 g.cm^-3, F(000)=1428,μ(Mo-Kα)=0.589 mm^-1, R₁=0.0424, wR₂=0.0981. Basal structure of the complex is made of N'-acetyl-9-hydroxyl-9H-fluorene-9-carbohydrazide, cobalt atom and methanol molecule. In the title complex, Co(II) is coordinated by O1,O3 and N1 atoms from one of the N'-acetyl-9-hydroxyl-9H-fluorene-9-carbohydrazide ligand, O4,O6 and N3 atoms from the other N'-acetyl-9-hydroxyl-9H-fluorene-9-carbohydrazide ligand. The basal plane in the distorted octahedral consists of O4,N3,O6,O3,N1 and O1 atoms.Concentration-dilution method is used to test the bactericided activity of ligands and complexes against four fungoid (Staphylococcus aureus, Escherichia coli, Bacillus subtilis and Proteus vulgaris). 9-hydroxyl-9H-fluorene-9-carbohydrazide and complexes expressed almost activity on four fungoid. N'-acetyl-9-hydroxyl-9H-fiuorene-9-carbohy-drazide ligand and [Co(C₁₆H₁₃N₂O₃)₂]·2CH₃OH expressed evident activity on Bacillus subtilis of bacteria. [Cu(C₁₆H₁₃N₂O₃)₂]·CH₃OH expressed obvious activity on Proteus vulgaris of bacteria.