.2 - Alkoxycarbonyl-propyl Tin Synthesis, Characterization And Nature Of The Study

Organotin complexes have been used extensively as catalysts, stabilizers, biocides, anti-fouling agents and wood preservatives. In recent years, the investigations on the structure mode and biological activities, especially anti-tumor activity, of organotin complexes have become the focus on organometallic chemistry. In this thesis, more than 30 organotin related complexes were synthesized by using 2-carbomethoxypropylphenyltin chloride, 3-hydroxide radical-2-methylpropyl- phenyltin chloride as substrates which were prepared by 2-carbomethoxypro- pylphenyltin and 1,10-phenanthroline, 2,2'-bipyridine, dimethylformamide, sodium dithiocarbamate, potassium sulfocarbimide as ligands. They were characterized by IR, NMR spectra, elemental analysis, and two single crystal structures of the typical organotin complexes were determined. The variations on structure and property were also discussed. The thesis contains the following works.1. 2-Carbomethoxypropylphenyltin , Ph₃SnCH₂CH(CH₃)COOCH₃ was synthesized by the hydrostannation of methyl methacrylate with triphenyltin hydride which is the reduction product of Ph₃SnCl by LiAlH₄. A series of 2-carbomethoxypropyl- diphenyltin chloride, 2-carbomethoxypropylphenyltin dichloride, X_nPh_3-nSnCH₂CH(CH3)COOCH₃(n=1,2;X=Cl,Br,I)) were synthesized by Ph₃SnCH₂C(CH₃)COOCH₃ reacting with ICl, Br₂, I₂ and characterized by means of elemental analysis, IR, NMR spectra. The results show that the ester carbonyl oxygen atom was coordinated to the tin atom in the organotin complexes, and formed the intromolecular five-membered chelate rings structure. The transesterification of the compounds X_nPh_3-nSnCH₂CH(CH₃)COOCH₃ with an alcohol was studied, and the reaction mechanism of intramolecular Lewis acid catalysis were suggested.2. The reactions of the compounds X_nPh_3-nSnCH₂CH(CH₃)COOCH₃ with ligands,such as 1,10-Phenanthroline, 2,2'-Bipyridine, dimethyl sulfoxide, sodium dithiocarbamate and potassium sulfocarbimide, were studied. A series of organotin complexes were prepared and characterized by elemental analysis, IR, NMR spectra. The results show that in the 1:1 type complexes with monodentate ligands such as dimethyl sulfoxid and potassium sulfocarbimide, the oxygen of carbonyl group was still coordinated to tin. However, in the 1:2 complexes with monodentate ligands and the complexes with bidentate ligands, such as 1,10-Phenanthroline, 2,2'-Bipyridine, sodium dithiocarbamate, the carbonyl groups coordination to tin were replaced by the ligands. to make the C=O groups free. So all the complexes were six-coordinated. The crystal structure of the complex, PhSn(CH2CH(CH3)CO2Me)(S2CN(C2H5)2)(NCS), was determined. The results indicate that the complex belonged to monoclinic system, P 2j/a group, and the crystal data were as follows: CnH^i^C^SaSn, Mr = 503.25, a = 8.8041(10), b = 20.142(2), c= 12.7430(15) A, P =102.716(2)°, V = 2204.3(4) A3, Z = 4, Dc= 1.516 g/cm3, \i = 1.455 mm'1, F(000)= 1016.3. A series of 3-hydroxyl-2-methylpropylphenyltin chloride, XnPli3_nSnCH2CH-(CH3)CH2OH (n = 1, 2; X= Cl, Br, I), were synthesized by the reaction of IC1, Br2 and I2 with Ph3SnCH2CH(CH3)CH2OH obtained by reduction of Ph3SnCH2CH(CH3)COOCH3 with LiAlH4, and characterized by means of elemental analysis, IR, NMR spectra. The results show that the hydroxyl oxygen atom was coordinated to the intramolecular tin atom in the compounds, and formed the intramolecular five-membered chelate rings structure. The crystal structure of the compound, Ph2ISnCH2CH(CH3)CH2OH, was determined. The results indicate that the compound belonged to triclinic system, P -1 space group, and the crystal data were as follows: Ci6H]6IOSn, Mr=469.88, a = 9.6200(4), b = 9.6262(4), c = 10.2421(4)A, a = 96.582, p =97.846, y=108.301°,V = 879.46(6) A3, Z = 2, Dc= 1.774 g/cm3, n =3.199 mm'1, F(000)=446.4. The reactions of the compound 3- hydroxyl -2-methylpropylphenyltin chloride, XnPh3-nSnCH2CH(CH3)CH2OH (n =1, 2; X = Cl, Br, I) with ligands, such as...