官能基取代烃基锡及其羧酸酯配合物的合成、表征和性质研究

【作者】 毛武涛；

【导师】 田来进；

【作者基本信息】 曲阜师范大学 ， 无机化学， 2007， 硕士

【摘要】 官能基取代烃基锡因为具有配位能力的杂原子，配位原子复杂多变的配位方式导致了这一类有机锡丰富多彩的结构。各类有机锡羧酸酯包括二硫代羧酸酯更是因为其各式各样的结构模式而成为当今研究的热点。它们被广泛应用于催化、材料、农药、医药等领域。本文合成了含有氨基甲酰基、酯基、羟基等不同官能基的四个不同系列的有机锡，并以它们为底物和N—取代氨基酸和二硫代氨基甲酸盐作用合成了四个不同系列的官能基取代烃基锡羧酸酯配合物，共计80多个未见文献报道的化合物。利用元素分析、红外、核磁等手段表征了其结构，解析了其中16个化合物的晶体结构。测定了每个系列代表性化合物的抑菌活性及个别化合物的抗肿瘤活性，并初步探讨了其构效关系。本文由一下内容组成：1．首先由三苯基氢化锡和丙烯酰氨反应然后和各种卤素作用得到系列有机锡：Ph_3-nX_nSnCH₂CH₂CONH₂（X=Cl，Br，I；n=1，2）。进一步合成了它们的羧酸酯配合物：Ph_3-nX_n-1SnCH₂CH₂CONH₂（OOCCHRNHCOC₆HF₄）（R=H，Me.Bn）、Ph_3-nX_n-mSnCH₂CH₂CONH₂（S₂CWR₂¹）_m（m=1，2；R¹=Me，Et等）。解析了化合物：Ph₂ClSnCH₂CH₂CONH₂、Ph₂ISnCH₂CH₂CONH₂、PhBr₂SnCH₂CH₂CONH₂、PhClSnCH₂CH₂CONH₂（S₂CNEt₂）、PhSnCH₂CH₂CONH₂（S₂CNEt₂）₂、PhSnCH₂CH₂CONH₂（S₂CNMe₂）₂的晶体结构，并结合波谱方法讨论了其配位模式和结构特点。2．用类似的方法合成了γ-羟基丙基苯基卤化锡及其二硫代氨基甲酸酯系列配合物：Ph_3-nX_nSn（CH₂）₃OH、Ph_3-nX_n-mSn（CH₂）₃OH（S₂CNR₂¹）_m（m=1，2；R¹=Me，Et等）。解析了Ph₂BrSn（CH₂）₃OH、Ph₂BrSn（CH₂）₃OH（S₂CNEt₂）、Ph₂ClSn（CH₂）₃OH（S₂CNEt₂）、Ph₂ClSn（CH₂）₃OH（S₂CNMe₂）、PhSn（CH₂）₃OH（S₂CNEt₂）₂等化合物的晶体结构。数据显示，有机锡底物往往具有分子内配位的五元环结构，而在配合物中这种结构或多或少的被破坏。3．同样的方法合成了β-环戊酯基乙基苯基卤代锡、β-环戊酯基乙基三氯代锡以及β-环戊酯基乙基三氯代锡的二硫代氨基甲酸酯配合物：Cl₃SnCH₂CH₂CO₂C₅H₉、Ph_3-nX_nSnCH₂CH₂CO₂C₅H₉（X=Cl，Br，I；n=1，2）、Cl_3-nSnCH₂CH₂CO₂C₅H₉（S₂CNR₂¹）_n（n=1，2，3）。解析了化合物：PhCl₂SnCH₂CH₂CO₂ C₅H₉、Cl₃SnCH₂CH₂CO₂ C₅H₉、（Et₂NCS₂）₃SnCH₂CH₂CO₂C₅H₉的晶体结构。分析了配体的配位方式对化合物结构的影响。4．利用三苯基氢化锡和乙炔基金刚烷醇加成制备了2—[2-（三苯基锡基）乙烯基]金刚烷醇，测试并解析了反式异构体晶体结构。5．利用微量量热法测定了每种官能基取代烃基锡和它们羧酸酯配合物中代表性化合物的对大肠杆菌的抑菌活性，并讨论这些化合物中抑菌活性的变化规律。数据显示所有的有机锡化合物都有较好抑菌活性，而且不同的官能基对抑菌活性具有显著的影响。Ph₂ClSnCH₂CH₂CONH₂，Ph₂BrSnCH₂CH₂CH₂OH，Ph₃SnCH=CH（ADM-2-OH）对C6和A549细胞的抑制数据显示其具有良好的抗肿瘤活性更多还原

【Abstract】 It is obviously that functionally-substituted alkylstannanes have many heteroatoms with co-ordinating abilities. Because of the complexing coordination medel of the hetertoatoms, rich and colorful structures of this type organotin appeare. In the case of the instinsic intrest ,oganotin carboxylates including organotin dithiocarbamate have become the hot area of reseach. They have been proverbially applying to catalytic, material, pesticide, curatorial areas. In this dissertation, four diferent types of functionally-substituted alkylstannanes were prepared , they had amido-cyl, alkoxycarbinic, hydroxyl, organic group respectively. Furtherly,four different types of oganotin carboxylateswere synthized, using the types of functionally-substituted alkylstannanes as subtrate to act with N-substuted amino acids and aminodithioformic acids, adding up to less than 80 compands. They were characterized by IR, NMR spectra, and 16 single structures of the typical organotin compands were determined. The antibascterial and antitumor activity of some tipical compads of every sery organotins were determined by minicalorimetry method, and possible relation between the activity and the defent structures were analylized. The dissertation contains the following works.1.Seris organotins can be abtained after treating the product synthylized by the action of triphylstanne and acylamine with halogens: Ph_3-nX_nSnCH₂CH₂CONH₂ （X=Cl,Br,I;n=1,2）. Furtherly, a number of compexes were prepared: Ph_3-nX_n-1SnCH₂CH₂CONH₂（OOCCHRNHCOC₆HF₄） （R=H,Me.Bn）,Ph_3-nX_n-mSnCH₂CH₂CONH₂（S₂CNR¹₂）m （m=1,2;R¹=Me,Et）. The crystal structures of : Ph₂ClSnCH₂CH₂CONH₂, Ph₂ISnCH₂CH₂CONH₂, PhBr₂SnCH₂CH₂CONH₂, PhClSnCH₂CH₂CONH₂（S₂CNEt₂）,PhSnCH₂CH₂CONH₂（S₂CNEt₂）₂, PhSnCH₂CH₂CONH₂（S₂CNMe₂）₂ were resolved and their coordination mode and structural features were discussed by combining spectroscopic analysis.2.With the same methed,γ-hydroxylpropyl-phylstanne halides and their dithiocarbamate were synthesized: Ph_3-nX_nSn（CH₂）₃OH,Ph_3-nX_n-mSn（CH₂）₃OH（S₂CNR¹₂）_m（m=1,2;R¹=Me,Et）. The crystal structures of these compands: Ph₂BrSn（CH₂）₃OH, Ph₂BrSn（CH₂）₃OH（S₂CNEt₂）, Ph₂ClSn（CH₂）₃OH（S₂CNEt₂）, Ph₂ClSn（CH₂）₃OH（S₂CNMe₂）,PhSn（CH₂）₃OH（S₂CNEt₂）₂ were deter determined. The date reals that most of the subtrate organotin compands of this series have a five-numbered ring structure, as the result of the intramolecular coordination. However, in the complexes the intramolecular coordination was wrecked, leading to the disappearing of five-numbered ring structure.3. A series ofβ-alkoxycarbonylethylphenyltin halides, Cl₃SnCH₂CH₂CO₂Cp, Ph_3-nX_nSnCH₂CH₂CO₂Cp （X=Cl,Br,I;n=1,2）. and their dithiocarbamates, Cl_3-nSnCH₂CH₂CO₂Cp（S₂CNR¹₂）_n（n=1,2,3） were synthesized and characterized. The crystal structures of 3 compandes: PhCl₂SnCH₂CH₂CO₂C₅H₉), Cl₃SnCH₂CH₂CO₂ C₅H₉, （Et₂NCS₂）₃SnCH₂CH₂CO₂ C₅H₉ were determined.4. 2-[2-（triphyltin）-vinyl]adamantanol was prepeared through the addition action between tripylstanne and ethyl- adamantanol. The date of the products X-diffraction demonstrates that qulity of cis-isomer is more than trans-isomer.5. The antibascterrial activity of a number of compands of every series of functionally-substituted alkylstannanes and teir carboxylate complexes were determined by the minimcalorimetry methed, and possible relation between the activity and the defent structures were analylize.Bioassay results have shown that compound Ph₂ClSnCH₂CH₂CONH₂ , Ph₂BrSnCH₂CH₂CH₂OH, Ph₃SnCH=CH（ADM-2-OH）, possess good in vitroantitumor activity against tumor cells C6 and A549.更多还原