3-(2,4,6-triisopropylphenyl)-3-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-5,5-diphenyl-1,2,4,3-triselenastannolane | 144602-86-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 3-(2,4,6-triisopropylphenyl)-3-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-5,5-diphenyl-1,2,4,3-triselenastannolane
• CAS: 144602-86-8
• 化学式: C₅₅H₉₂Se₃Si₆Sn
• 分子量: 1277.44
• InChiKey: JJIITZTUDSWVLS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  15.07
• 重原子数：
  65.0
• 可旋转键数：
  16.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  3-(2,4,6-triisopropylphenyl)-3-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-5,5-diphenyl-1,2,4,3-triselenastannolane 在 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
• 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 作用下， 以 四氢呋喃 为溶剂， 以63%的产率得到3-(2,4,6-triisopropylphenyl)-3-{2,4,6-tris(bis(trimethylsilyl)methyl)phenyl}-5,5-diphenyl-1,2,4,3-triselenastannolane
  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

• The first stable 1,2-thiastannete and 1,2-selenastannete: their syntheses and crystal structures
  作者：Norihiro Tokitoh、Yasusuke Matsuhashi、Renji Okazaki

  DOI：10.1039/c39930000407

  日期：——

  Thermal decomposition of overcrowded 1,2,4,3-trichalcogenastannolanes 1 resulted in the formation of the first stable 1,2-chalcogenastannete derivatives 3via[2 + 2]cycloaddition of intermediary stannanethione and stannanselone 2; the molecular structures of 3 were determined by X-ray crystallographic analysis.

  过度拥挤的 1,2,4,3-三钙原石杉烷 1 受热分解后，通过中间体石杉硫酮和石杉硒酮 2 的[2 + 2]环加成，形成了首个稳定的 1,2-三钙原石杉烷衍生物 3；通过 X 射线晶体分析法确定了 3 的分子结构。