2-chloro-2,2,4,4-tetramethyl-1-oxa-3-chlora-2,4-distannacyclobutane dimer | 85990-37-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2-chloro-2,2,4,4-tetramethyl-1-oxa-3-chlora-2,4-distannacyclobutane dimer
• 英文别名: carbanide;oxygen(2-);tin(4+);tetrachloride
• CAS: 85990-37-0
• 化学式: C₈H₂₄Cl₄O₂Sn₄
• 分子量: 768.929
• InChiKey: SPLSGIVEPWGNKV-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -10.14
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2-chloro-2,2,4,4-tetramethyl-1-oxa-3-chlora-2,4-distannacyclobutane dimer 、 盐酸多巴胺 以 甲醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  基于氧桥锡（IV）簇的独特可关闭荧光传感器的合成和结构阐明，用于选择性检测生物体液中的多巴胺

  摘要：

  合成了氧桥联的 Sn (IV) 簇 (TOC)，并通过 FT-IR、UV-vis、1 H NMR、119 Sn NMR、质谱和单晶 X 射线衍射研究对其进行了充分表征。单晶X射线分析表明，该晶体结晶为具有P 21/c 空间群的单斜晶系，并表现出扭曲的三角双锥几何形状。TOC 表现出独特的关闭荧光响应，可选择性检测多巴胺 (DA) 而非其他分析物。使用乔布图计算 TOC 和 DA 之间的化学计量。检测限值为 1.33 µM。对晶体结构进行 Hirshfeld 表面分析，研究分子中的 HH、Cl-H、Cl-Cl、Sn-Cl 和 Cl-C 相互作用研究。密度泛函理论（DFT）研究进一步支持了传感机制，这与实验结果非常吻合。此外，TOC化学传感器被用来检测人血浆中的DA，分子对接研究验证了化学传感器和蛋白质之间的相互作用。进行了共焦荧光成像研究并验证了人血浆中 DA 的 TOC 传感能力。

  DOI：

  10.1016/j.saa.2023.123152
• 作为产物：
  描述：

  1,2-dichlorotetramethyldistannane 在 氧气 作用下， 以 环己烷 为溶剂， 生成 2-chloro-2,2,4,4-tetramethyl-1-oxa-3-chlora-2,4-distannacyclobutane dimer
  参考文献：
  名称：

  溶液中锡烷环戊-3-烯的光解直接检测，二聚化和化学捕集二甲基锡和二苯基锡

  摘要：

  Dimethyl- and diphenylstannylene (SnMe2 and SnPh2, respectively) have been successfully detected and characterized in solution. The stannylenes were generated by photolysis of 1,1,3trimethy1-4-phenyl- (2) and 3,4-dimethy1-1,1-diphenylstannacydopent-3-ene (3), respectively, which have been shown to extrude the species cleanly and in high (0.6 < Phi <0.8) quantum yields through trapping studies using dichlorodimethylstannane (Me2SnCl2) as the stannylene substrate. Laser flash photolysis of 2 and 3 in deoxygenated hexanes affords promptly formed transient absorptions assigned to SnMe2 (lambda(max) = 500 nm; epsilon(500) = 1800 +/- 600 M-1 cm(-1)) and SnPh2 (lambda(max) = 290, 505 nm; 8500 = 2500 +/- 600 M-1 cm(-1)), respectively, which decay with absolute second-order rate constants within a factor of 2 of the diffusional limit in both cases. The decay of the stannylenes is accompanied by the growth of new transient absorptions ascribable to the corresponding dimers, the structures of which are assigned with the aid of DFT and time-dependent (TD) DFT calculations at the (TD)omega B97XD/6-31+G(d,p)(C,H,O)-LANL2DZdp(sn) level of theory. Dimerization of SnMe2 affords a species exhibiting lambda(max) = 465 nm, which is assigned to the expected Sn=Sn doubly bonded dimer, tetramethyldistannene (Me2Sn=SnMe2, 16a), in agreement with earlier work. In contrast, the spectrum of the dimer formed from SnPh2 exhibits strong absorptions in the 280-380 nm range and a very weak absorption at 650 nm, on the basis of which it is assigned to phenyl(triphenylstanny)stannylene (17b). The calculations suggest that 17b is formed via ultrafast rearrangement of a novel phenyl-bridged stannylidenestannylene intermediate (20), which can be formed either directly by "endo" dimerization of SnPh2 or by isomerization of the "exo" dimer, tetraphenyldistannene (16b); the predicted barriers for these rearrangements are consistent with the experimental finding that the observed product is formed at close to the diffusion-controlled rate. Absolute rate and equilibrium constants are reported for the reactions of SnMe2 and SnPh2 with Me2SnCl2 and methanol (MeOH), respectively, in hexanes at 25 degrees C.

  DOI：

  10.1021/acs.organomet.5b00615

文献信息

• A novel route for the preparation of dimeric tetraorganodistannoxanes
  作者：Jens Beckmann、Dainis Dakternieks、Fong Sheen Kuan、Edward R.T Tiekink

  DOI：10.1016/s0022-328x(02)01705-9

  日期：2002.10

  The reaction of polymeric diorganotin oxides, (R2SnO)n (R=Me, Et, n-Bu, n-Oct, c-Hex, i-Pr, Ph), with saturated aqueous NH4X (X=F, Cl, Br, I, OAc) in refluxing 1,4-dioxane afforded in high yields dimeric tetraorganodistannoxanes, [R2(X)SnOSn(X)R2]2, and in a few cases diorganotin dihalides or diacetates, R2SnX2. The reported method appears suitable for the synthesis of fluorinated tetraorganodistannoxanes

  聚合二有机锡氧化物的反应中，（R 2的SnO）Ñ（R =甲基，乙基，Ñ -Bu，Ñ -辛，Ç -六角，我-Pr中，Ph），用饱和含水NH 4 X（X = F， Cl，Br，I，OAc）在回流的1,4-二恶烷中以高收率得到二聚四有机二锡锡烷，[R 2（X）SnOSn（X）R 2 ] 2，在少数情况下，二有机锡二卤化物或二乙酸酯为R 2 SnX 2。报道的方法似乎适用于氟化四有机二锡氧烷的合成。鉴定[R 2（OH）SnOSn（X）R 2 ] 2（R =n -Bu; X = Cl，Br）和[R 2（OH）SnOSn（X）R 2 ] [R 2（X）SnOSn（X）R 2 ]提出了从[R 2（OH）SnOSn（OH）开始的系列取代机制R 2 ] 2。X射线晶体结构测定报告为[我2（ACO）SnOSn（OAC）Me 2 ] 2（29A），[我-Pr 2（BR）SnOSn（BR）我-Pr 2 ] 2（20A），[
• Synthesis, Characterization and Reactivity of a Diorganotin Thiocarboxylate: Dimethyl(thioacetato)-tin(IV) Chloride and its Reactions with Nucleophiles Exhibiting Desulfurization
  作者：Neetu Singh、Subrato Bhattacharya、Heinrich Nöth、Peter Mayer

  DOI：10.1515/znb-2009-0116

  日期：2009.1.1

  Dimethyl(thioacetato)tin chloride (1) was synthesized by the reaction of dimethyltin dichloride with thioacetic acid in the presence of triethylamine. Compound 1 was subjected to hydrolysis under different reaction conditions in order to obtain sulfido/hydrosulfidotin compounds. Except for one case where the product was hexamethyl-1,3,5-trithia-2,4,6-tristannacyclohexane, (Me2SnS)3 (4), all other reactions led to desulfurization, and the products obtained were organostannoxane compounds, dinuclear tetramethyl-oxo-dichloroditin, Me₂SnCl₂.Me₂SnO} ₂ (2), and tetraacetatodioxotetra( dimethyltin), (Me₂Sn)₄O₂(O₂CMe)₄ (3). These complexes have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR and FTIR spectroscopy, and compounds 2 - 4 also by X-ray crystallography. Density functional calculations were performed to explain the structure and reactivity of the compounds.

  Dimethyl(thioacetato)tin chloride (1)是通过二氯二甲基锡与硫代乙酸在三乙胺存在下反应合成的。化合物1在不同的反应条件下进行水解，以获得硫/氢硫代锡化合物。除了一个情况下生成了六甲基-1,3,5-三硫代-2,4,6-三锡环己烷(Me2SnS)3 (4)之外，所有其他反应均导致了脱硫，得到的产物是有机锡氧化合物，二核四甲基-氧化二氯代锡(Me2SnCl2.Me2SnO)2 (2)，和四乙酸二氧代四(二甲基锡) (Me2Sn)4O2(O2CMe)4 (3)。这些配合物通过1H、13C、119Sn核磁共振和傅里叶变换红外光谱进行了表征，化合物2-4还通过X射线晶体学进行了表征。密度泛函计算用于解释化合物的结构和反应性。