2-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-2-(2,4,6-triisopropylphenyl)-4-phenyl-1,3,2-oxaselenastannolane | 170703-59-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-2-(2,4,6-triisopropylphenyl)-4-phenyl-1,3,2-oxaselenastannolane
• 英文别名: 2-tris[bis(trimethylsilyl)methyl]phenyl-2-(2,4,6-triisopropylphenyl)-4-phenyl-1,3,2-oxaselenastannolane
• CAS: 170703-59-0
• 化学式: C₅₀H₉₀OSeSi₆Sn
• 分子量: 1073.45
• InChiKey: UOJUNGVFSUDFGC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  14.6
• 重原子数：
  59.0
• 可旋转键数：
  15.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  3-(2,4,6-triisopropylphenyl)-3-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-6,6-diphenyl-1,2,4,5-tetraselena-3-stannacyclohexane 在 HMPT 、 triphenylphosphine 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 2-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-2-(2,4,6-triisopropylphenyl)-4-phenyl-1,3,2-oxaselenastannolane
  参考文献：
  名称：

  Formation and reactions of stannanethiones and stannaneselones

  摘要：

  Two approaches for the formation of stannanethiones and stannaneselones were examined, i.e., (i) the thermal retrocycloaddition of trichalcogenastannolanes 1 and (ii) the dechalcogenation of tetrachalcogenastannolanes 2 and 3. Novel heterocycles containing tin and chalcogen atoms, 1,2,4,3-trichalcogenastannolanes Tb(Tip)SnY3CPh2 [1a,b (Y = S, Se; Tb = 2,4,6-tris[bis-trimethylsilyl)methyl]phenyl; Tip = 2,4,6-triisopropylphenyl)], have been synthesized by the thermal reaction of 1,2,3,4,5-tetrachalcogenastannolanes Tb(Tip)SnY4 (3) with diphenyldiazomethane followed by dechalcogenation with hexamethylphosphoric triamide. Thermal decomposition of trichalcogenastannolanes 1 in the presence of dimethyl acetylenedicarboxylate (DMAD) afforded thiastannete 8 and selenastannete 14 as novel tin-containing heterocycles. The formation of 8 and 14 was explained in terms of a [2 + 2]cycloaddition of intermediary stannanethione 18a and stannaneselone 18b with DMAD. Dechalcogenation of tetrachalcogenastannolanes 2 and 3 with trivalent phosphorus compounds in the absence of trapping agents gave dichalcogenadistannetanes whose formation was explained in terms of dimerization of stannanethione 18a or stannaneselone 18b, except for the reaction of more crowded triisopropylphenyl-substituted 3a which gave a monomeric product 28 at room temperature on account of a slower rate of dimerization. The desulfurization of 3a with triphenylphosphine in the presence of an excess amount of 2,3-dimethyl-1,3-butadiene provided [4 + 2]cycloadduct 32 as the first example of [4 + 2]cycloaddition of a stannanethione. The structures of 26, 27, 31, 8, and 14 were definitely determined by X-ray diffraction analysis. The central four-membered rings of trans-dichalcogenadistannetanes 26 and 31 were almost completely planar, while those of cis-27 had unprecedentedly large fold angles due to the steric repulsion between two Tb groups. Both 8 and 14 were found to have distorted trapezoid skeletons reflecting the coexistence of long tin-chalcogen bonds and short carbon-carbon double bonds.

  DOI：

  10.1021/om00031a030

文献信息

• Reaction of Tetrachalcogenastannolanes with Triphenylphosphine. A Novel Mode of Generation for Overcrowded Stannanethiones and Stannaneselones
  作者：Norihiro Tokitoh、Yasusuke Matsuhashi、Midori Goto、Renji Okazaki

  DOI：10.1246/cl.1992.1595

  日期：1992.8

  Dechalcogenation of overcrowded 1,2,3,4,5-tetrachalcogenastannolanes with triphenylphosphine resulted in the formation of the corresponding 1,3,2,4-dichalcogenadistannetanes via [2+2]cycloaddition of intermediary stannanethione and stannaneselone. Molecular structures of the newly obtained 1,3,2,4-dichalcogenadistannetanes were examined by X-ray analysis.

  用三苯基膦对过度拥挤的 1,2,3,4,5- 四羰基甾烷醇进行脱羰基化反应，通过中间体斯坦尼硫酮和斯坦尼硒酮的 [2+2]cycloaddition 生成相应的 1,3,2,4- 二羰基阿地斯塔尼烷。通过 X 射线分析研究了新获得的 1,3,2,4-二羰基双十四烷的分子结构。
• Okazaki, Renji; Tokitoh, Norihiro; Ishii, Akihiko, Phosphorus, Sulfur and Silicon and the Related Elements, 1992, vol. 67, # 1-4, p. 49 - 66
  作者：Okazaki, Renji、Tokitoh, Norihiro、Ishii, Akihiko、Ishii, Naoko、Matsuhashi, Yasusuke、et al.

  DOI：——

  日期：——
• Synthesis and reactions of stanneneselone
  作者：Masaichi Saito、Norihiro Tokitoh、Renji Okazaki

  DOI：10.1016/0022-328x(95)00334-m

  日期：1995.9

  Stannaneselone Tbt(Tip)Sn=Se (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phe Tip = 2,4,6-triisopropylphenyl), a novel compound containing a tin-selenium double bond was synthesized by the reaction of the corresponding stannylene Tbt(Tip)Sn with elemental selenium. It reacted with phenyl isothiocyanate, mesitonitrile oxide and styrene oxide to afford cycloadducts. In the reaction with phenyl isothiocyanate, 1,3,2-dithia- and diselenastannetanes were obtained instead of the expected 1,3,2-thiaselenastannetane. Another approach to the stannaneselone by deselenation of the corresponding 1,2,3,4,5-tetraselenastannolane with triphenylphosphine is also described.