Synthesis And Properties Of Hydroxycoumarin And Its Organotin Derivatives

Coumarin is a kind of aromatic oxygen heterocyclic compound containing benzo-?-pyrone structure,and has wide application in the fields of perfumery,optics and pharmacy.Organotin compounds are a class of organometallic compounds with diverse structures and good biological activity.A series of synthesized coumarin-organotin compounds can achieve the synergistic effect of multi-component properties and obtain excellent optical and pharmaceutical materials.In this paper,by hydroxycoumarin reacting with organotin chloride or oxide,functional groups such as fluorine atom,coumarin and Schiff base are combined into organotin molecules to synthesize 49 compounds with novel structures.The structures of organotin compounds have been characterized by elemental analysis,nuclear magnetic resonances(¹H?¹³C and ¹⁹F),infrared and X-ray single crystal diffraction techniques,and their photophysical properties?UV and fluorescence?and anticancer activity were preliminarily studied.A series of 7-hydroxy-4-alkyl coumarins?alkyl group R=CH₃,CF₃,C₆H₅,C₆HF₄?were obtained by the reaction of resorcinol with ethyl acylacetate under p-toluenesulfonic acid,followed by triorganotin hydroxide R?₃SnOH,bis?triorganotin?oxide?R?₃Sn?₂O(R?=n-C₄H₉,C₆H₅,c-C₆H₁₁,C₆H₅C?CH₃?₂CH₂)and dibutyltin oxide,20 new 7-hydroxycoumarin organotin derivatives were synthesized and characterized.The crystal structures show that the tin atom of the triorganotin compound is pentacoordinated and has a distorted triangular bipyramid configuration in which three alkyl groups are located at a triangular plane,a phenol oxygen atom and a carbonyl group oxygen atom of coumarin lactone ring of adjacent molecule.Oxygen atoms occupy the axial positions and form a one-dimensional chain structure.The ultraviolet absorption and fluorescence emission wavelengths of the ligand and the tin compound are respectively at³35 nm and⁴30 nm,but the absorption intensity of the tin complexes is significantly increased compared with the ligand.These organotin compounds can be used as blue fluorescent materials.The anticancer activity of the ligands and tin compounds showed that the anticancer activity of the ligand was weak(IC₅₀?29?100?M),and the tin compounds had strong anticancer activity(IC₅₀⁰.4?0.01?M),which was stronger than clinical cis-platin..Undertheactionofmagnesiumethoxide,theself-madeethyl2,3,4,5-tetrafluorobenzoylacetate was acylated with an acid chloride,then the enol reacted intramolecularly with the fluorine atom to synthesize four kinds of 2-hydrocarbyl-3-ethoxycarbonyl-6,7,8-trifluorochromone.The chromones are hydrolyzed in aqueous ammonia to form 3-acyl-4-hydroxy-6,7,8-trifluorocoumarin.The reaction of 3-acetyl-4-hydroxy-6,7,8-trifluorocoumarin with an organotin oxide or hydroxide gives five corresponding organotin derivatives.Sixschiffbasesofhydrazidewereobtainedbyreactionof3-acetyl-4-hydroxy-6,7,8-trifluorocoumarin with hydrazide RCONHNH₂?R=CH₃,C₆H₅,C₄H₃S,4-Py,4-ClC₆H₄,4-OHC₆H₄?,and then reacted with the diorganotin chloride R?₂SnCl₂?R?=CH₃,C₂H₅,n-C₄H₉,C₆H₅?.Finally,24 new Schiff base organotin compounds containing fluorocoumarin hydrazide were obtained.Structural characterization confirmed that a five-membered chelating ring and a six-membered chelating ring were formed by combining tridentate ONO ligands in the enol form with tin atoms.Crystal structures show that acetyl hydrazone dimethyltin compound forms the four-member ring structure unit containing Sn₂O₂bridging dimers,4-pyridine formyl hydrazone tin compound formed one dimensional zigzag chains through coordination of pyridine nitrogen atom to tin atom of the adajcent molecule,4-chlorobenzene formyl hydrazone diphenyltin compound forms a dimensional chain structure by using the carbonyl oxygen of coumarin lactone ring coordination to tin.The maximum absorption wavelength of the hydrazide Schiff base ligands is at 330 nm,the wavelength of the tin compounds is red-shifted,and the maximum absorption wavelength is at³80 nm,and the absorption intensity is significantly increased.The fluorescence emission wavelength of the ligands and the tin compounds is at⁵30 nm,whereas the emission intensity of the complex is remarkably increased.They can be used as yellow-green fluorescent materials.The anticancer activities of the ligands and tin compounds were determined.The results showed that the anticancer activities of the ligands were weak(IC₅₀?29?100?M),while the tin compounds had strong anticancer activities(IC₅₀¹.5?0.4?M).In this work,we explored the method of synthesizing chromones by the intramolecular enol nucleophilic replacing F atom and 4-hydroxyl coumarin compounds.A series of the chromones,hydroxycoumarins and the corresponding organotin derivatives were synthesized and characterized.Their photophysical properties and anticancer activities were studied.This work enriched the content of chromone,coumarin and organotin chemistry,and laid the experimental foundation for further development of its application.