Of ¦Á, ¦Â-unsaturated Carbonyl Compounds Of Tin Chloride Synthesis, Structure, Properties And Reaction

Because of organotin compounds?biological activity, especially organotin complexes?anti-tumour activity,the studies in recent years on organotin complexes have increased rapidly.But there are few reports on a, f3 梪nsaturated carbonyltin chloride.Jn order to investigate the biological activity of organotin complexes deeply, probe into the relationship of confirmation, it is necessary to synthesize a variety of organotin compounds. In the present note we are reporting the synthesis and characterization of a series of a, P 梪nsaturated carbonyltin chloride. We investigated the reaction of tin( II) chloride or tin with 2,4-pentanedione when acetyl chloride exists,and discuss the effect of solvent, acyl chloride and temperation to reaction. As a reault we have synthesized a series of a , P 梪nsaturated carbonyltin trichloride and dichloride when solvent is ether and acetyl chloride exists at 2O梸3O0C. Moreover, we have studied the mechanism of this reaction and discovered that the occurrence of the reaction lies on the hydrogen in the center of two carbonyls of 1 ,3-dione. In regard to complately substituted 1,3-dione, we can not gain target molecule. If the space obstruction of end group is big, only the reaction between SnC12 and 1 ,3-dione can occur. We have synthesized six a , P 梪nsaturated carbonyltin trichloride(five have not been reported) with corresponding 1,3-dione. We have synthesized four a , p 梪nsaturated carbonyltin dichloride(all have not been reported) with corresponding 1,3-dione. Fourteen new a , P 梪nsaturated carbonyltin complexes were synthesized by the reaction of gained a, P 梪nsaturated carbonyltin trichloride with five salicylideneanilines schiff bases and DMSO. Six a , P 梪nsaturated carbonyltin trichlorides ~. four a , P ?unsaturated carbonyltin dichlorides and fourteen a, P 梪nsaturated carbonyltin complexes have been characterized on the basis of elementary analysis,1 HNMR,IR,UV. The data of JR indicates that there is a carbonyl absorption at about 1640cm1.This effect is consistent with carbonyl oxygen-to-tin coordinated bond. In complexes carbonyl absorption shows at I63O~ 1640 cm1,so intramolecular carbonyl oxygen coordination is also exist. Because there exists intense H-Bond in schiff bases, there is no 3400 cm?absorption in schiff bases complexes.The coordinated ability of nitrogen of azomethine(-N=cH-) is reduced, on the contrary, phenolic hydroxyl抯 intensified. There is no obvious change about absorption of azomethine(-N=CH-) stretching modes between in coordination (1595 1605cm1) and in free ligand(1610 1603cm?.This also indicates that coordinated atom is not nitrogen of azomethine(-N=CH-).In complexes of schiff bases the existence of absorption[(Sn桹)5 11 ?13 cm抅 also shows that the ligand coordination to tin atom via phenolic oxygen atom. The stretching vibrated frenquency of S=O in DMSO vibrate from 1047 cm1(dissociated) to 990 cm?ll )(coordination),930 cm? 1 8)(coordination),940 cm?(22)(coordination). This is the result of oxygen-to-tin coordination. The data of UV indicates that the absorption of the Schiff bases,free ligands,at (303~1 0)nm, has been assigned to the azomethine(-N=cH-) n梸 J?* transition The signal due to the 憈 梸 ~t * transition of benzenoidat(303~4 )nm,(269?I )nm,(228~ 1 )nm. In the relative coordinations the data is constant. On the basis of the above, we considered that there is no N梸Sn band in the coordination.The signal(224.9nm)due to n梑 ~t * transition of DM50. In regard to 2梥ubstituted a, ~ 梪nsaturated carbonyltin trichlo...