1-phenylsulfonyl-2-phenyl-2-trimethylsilylethane | 89333-88-0

• 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: 1-phenylsulfonyl-2-phenyl-2-trimethylsilylethane
• 英文别名: Silane, trimethyl[1-phenyl-2-(phenylsulfonyl)ethyl]-；[2-(benzenesulfonyl)-1-phenylethyl]-trimethylsilane
• CAS: 89333-88-0
• 化学式: C₁₇H₂₂O₂SSi
• 分子量: 318.512
• InChiKey: FJPZZGIAWUWDKL-UHFFFAOYSA-N

物化性质

• 沸点：
  444.7±45.0 °C(Predicted)
• 密度：
  1.081±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.12
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-phenylsulfonyl-2-phenyl-2-trimethylsilylethane 在 正丁基锂 、 重水 作用下， 生成 [2-(Benzenesulfonyl)-2-deuterio-1-phenylethyl]-trimethylsilane
  参考文献：
  名称：

  A new silicon-mediated elimination–rearrangement

  摘要：

  Treatment of trimethylsilylethanes bearing alpha a-phenyl groups and beta-phenylthio, phenylsulfonyl or cyano groups with LDA causes elimination-rearrangement mediated by the beta-carbanionic species. Mechanistic conclusions are based on isotopic labelling experiments, the effects of substituents and approximate kinetics. These suggest that trimethylsilyl is the migrating group, that cleavage of the bond to the leaving group is little advanced in the transition structure and that placing of a substituent to encourage Si-C bond cleavage is mandatory.

  DOI：

  10.1039/p19960001511
• 作为产物：
  描述：

  硅烷,三甲基[1-苯基-2-[(苯基甲基)磺酰]乙基]- 在 ammonium heptamolybdate 、 偶氮二异丁腈 、 双氧水 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 24.0h， 生成 1-phenylsulfonyl-2-phenyl-2-trimethylsilylethane
  参考文献：
  名称：

  A new silicon-mediated elimination–rearrangement

  摘要：

  Treatment of trimethylsilylethanes bearing alpha a-phenyl groups and beta-phenylthio, phenylsulfonyl or cyano groups with LDA causes elimination-rearrangement mediated by the beta-carbanionic species. Mechanistic conclusions are based on isotopic labelling experiments, the effects of substituents and approximate kinetics. These suggest that trimethylsilyl is the migrating group, that cleavage of the bond to the leaving group is little advanced in the transition structure and that placing of a substituent to encourage Si-C bond cleavage is mandatory.

  DOI：

  10.1039/p19960001511

文献信息

• Protophilic versus silicophilic reactions in β-substituted silanes
  作者：Steven L. Jones、Charles J. M. Stirling

  DOI：10.1039/c39880001153

  日期：——

  in β-eliminations mediated by nucleophilic attack at silicon has been measured as a function of nucleophile, leaving group, and α-substituent; in some instances competition between protophilic and silicophilic reactions is observed.

  亲核攻击硅介导的β-消除反应的反应性已被测量为亲核试剂，离去基团和α-取代基的函数。在某些情况下，亲脂性和嗜硅性反应之间存在竞争。
• A new elimination–rearrangement involving silicon migration
  作者：Stefano Menichetti、Gwerydd Griffiths、Charles J. M. Stirling

  DOI：10.1039/c39920000054

  日期：——

  Lithium diisopropylamide (LDA), a strongly basic, poorly silicophilic nucleophile reacts with α-phenylsitanes bearing β-leaving groups to cause 1,2-silyl migration and loss of the leaving group.

  二异丙基酰胺锂（LDA）是一种碱性强、亲硅性差的亲核剂，它能与带有δ-离去基团的δ-苯基硅烷反应，导致 1,2-硅烷基迁移并失去离去基团。
• Menichetti; Stirling, Journal of the Chemical Society. Perkin Transactions 1 (2001), 2002, vol. 2, # 1, p. 28 - 30
  作者：Menichetti、Stirling

  DOI：——

  日期：——
• OCHIAI, MASAHITO;SUMI, KENZO;FUJITA, EIICHI;TADA, SHIN-ICHI, CHEM. AND PHARM. BULL., 1983, 31, N 9, 3346-3349
  作者：OCHIAI, MASAHITO、SUMI, KENZO、FUJITA, EIICHI、TADA, SHIN-ICHI

  DOI：——

  日期：——
• A new silicon-mediated elimination–rearrangement
  作者：Stefano Menichetti、Charles J. M. Stirling

  DOI：10.1039/p19960001511

  日期：——

  Treatment of trimethylsilylethanes bearing alpha a-phenyl groups and beta-phenylthio, phenylsulfonyl or cyano groups with LDA causes elimination-rearrangement mediated by the beta-carbanionic species. Mechanistic conclusions are based on isotopic labelling experiments, the effects of substituents and approximate kinetics. These suggest that trimethylsilyl is the migrating group, that cleavage of the bond to the leaving group is little advanced in the transition structure and that placing of a substituent to encourage Si-C bond cleavage is mandatory.