Synthesis And Properties Of Bis-?-diketone Derivatives Based On Resorcinol Structure

4,6-Diacetylresorcinol is a key raw material for the synthesis of a variety of organic heterocyclic systems.There are multiple active groups(hydroxyl and carbonyl)in its molecule.Its derivatives have a good applied prospect in organic synthesis,metal coordination,biological activity and pharmaceutical fields.In this paper,on the basis of the resorcinol,it would be modified first,and then transformed into seven bis-?-diketones by Claisen condensation,five bis-1H-pyrazoles derivatives,three europium(?)bis-?-diketonate complexes,and six difluoroboron bis-?-diketonate complexes.The properties of these compounds were characterized.It is divided into the following four parts:1. Using 4,6-diacetylresorcinol as raw material,at first it was modified by O-methylation,and then seven new bis-?-diketones(5a-5f and 7a)were synthesized by Claisen condensation.Their structures were confirmed by ~1H NMR,IR,EI-MS and UV-Vis spectrometry.The results showed that these bis-?-diketones existed in the form of enol in solution and solid state.2. Five new bis-?-diketones(5b-5f)were used to react with hydrazine hydrate and the bis-?-diketones were transformed into five new bis-1H-pyrazoles derivatives(6b-6f).Their structures were charaterized by ~1H NMR,IR,EI-MS spectrometry and their antimicrobial activities were studied by double tube dilution method.The results showed that the bis-1H-pyrazole 6e and 6f displayed a better antimicrobial activity.3. Using trifluoromethyl-bis-?-diketone(DPTD,7a)as the first ligand,three new binuclear europium(?)complexes(7b-7d)were synthesized by chelation reaction with europium trichloride hydrate using water,1,10-phenanthroline or 2,2'-Bipyridine as the secondary ligand,respectively.Their structures were confirmed by ~1H NMR,IR and elemental analysis.Their properties of the fluorescence and lifetime were studied by UV-vis absorption,fluorescence spectroscopy.It was found that europium(?)complex 7b displayed the stronger fluorescence intensity a longer lifetime(t=758ms).4. Six new difluoroboron bis-?-diketonate complexes were synthesized by chelation reaction of new bis-?-diketones with boron trifluoride ether.Their structures were confirmed by ~1H NMR,IR and EI-MS spectrometry.Their fluorescence properties were determined by UV-vis absorption and fluorescence spectroscopy.The results indicated that the difluoroboron bis-?-diketonate complex 8d exhibited the stronger fluorescence emission and the higher quantum yield(?=0.98).