| Organotin compounds have biological activity, especially the anti-tumour activity of organotin complexes, in recent years the studies on organotin compounds and organotin complexes have increased rapidly, a , 3 -unsaturated carbonyltin chloride is on the beginning. In order to investigate the structure and the biological activity of this sort of compounds better , probe into the relationship of structure and activity .study the influnce effectors of the reaction and the mechanism, it is necessary to synthesize new different structural organotin compounds. Thus , a series of a , 3 -unsaturated carbonyltin chloride and its complexes were synthesized and characterized. Whatsmore ,the reaction mechanism of the synthesized reaction was studied.In the reaction of 1,3-dione, SnCl2or Sn and acetyle chloride , the effect of different substituted groups was studied. The 1,3-di-tert-butyl-1,3-dione and 1,3-diphenyl-1,3-dione didn't react with SnClj or Sn .Because the substituted group in the two ends of 1,3-dione have big space obstruction. Otherwise , phenylformyl-acetone, 5,5-dimethyl-2,4-hexadione and 2-substituted 1,3-dione, only one big substituted group, could still react with SnCli or Sn. Conformation S-cis 2-acetylcycloketone also could react with SnCh and Sn , and we have gained the corresponding a , 3 -unsaturated carbonyltin chloride. With the synthesized 3-allyl-2,4-pentandione,2-acylcyclohexandione,2-acylcyclo-pentanone,phenylformylace tone,5,5-dimethyl-2,4-hexandione,2,2,6,6-tertmethyl-3,5-heptanone,diphenylformylmet hane and benzylacetonitrile. Only part of the 1,3-diones reacted successfully and five corresponding a , 3 -unsaturated carbonyltin trichlorides and four corresponding a , p -unsaturated carbonyltin dichlorides were synthesized. In order to make the study deeply, eight new complexes regarding to a , 3 -unsaturated carbonyltin trichlorides were synthesized. In this reaction, 2-allyl-l-methyl-buten-3-onyltin trichloride and 1 -methyl- l-butenyl-2-acetylcyclo-hexentin trichloride were choosed as sustrate and five salicylideneanilines Schiff bases as coordination ligands.The synthesized eighteen new compounds were characterized on the basis ofmelementary analysis, 1HNMR, IR, UV. a , P -unsaturated carbonyltin chlorides absorb at 1640-1650cm"1.It indicates that the exsistence of intramolecular carcbonyloxygen-to-tin coordinate bond. In the corresponding complexes the absorption also exist; The absorption of CH=N is about 1595-1610cm"1 and there is no absorption in Schiff bases complexes at 3400cm"1. This is the powerful proof of hydroxyl oxygen-to-tin coordination. The data of UV indicates that the absorption of the Schiff bases, about (343?)nm, has been assigned to the azomethine(-N=CH-) n^Ti* transition. There is no obvious change between Schiff bases and the relative coordination about the absorption of 71?TC* transition. On the basis of UV ,we considered that there is no N桽n bond in the coordination. Based on the data of 'HNMR,we have analyzed the complexes. Because a , p -unsaturated carbonyl displaced the chlorine atom of a ; g -unsaturated. a , 3 -unsaturated carbonyl displaced the chlorine atom of a , 3 -unsaturated carbonyltin dichlorides .It makes the electronic density of tin atom increased, The single peak of the a , g -unsaturated carbonyltin chloride which was synthesized through 2-acetylcyclone exists at 2.30ppm,so it must be the methyl in carbonyl. When bigger conjugated system between double linkage or benzene and carbonyl conformed, the chemical shift of alkenyl hydrogen increased to the value of benzene hydrogen; In di(l-tert-butyl-l-butenyl-3-one)dichloride, there are three hydrogens, single peak, exist at 2.58ppm. It should be the peak of carbonyl methyl. But other three hydrogens split. One exists at 2.00ppm, others exist at 2.24ppm.It should be hydrogen in alkenyl methyl judged from the value. At the same time, there are nine hydrogens in tert-butyl exist at l.Oppm, six at 1.06ppm, three at 1.26ppm. Alkenyl hydrogens are similar to the above ; one exists at 5.7... |
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