[2-[Bromo-(4-methylphenyl)sulfonylmethyl]phenyl]methyl-trimethylsilane | 203999-60-4

• 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-[Bromo-(4-methylphenyl)sulfonylmethyl]phenyl]methyl-trimethylsilane
• CAS: 203999-60-4
• 化学式: C₁₈H₂₃BrO₂SSi
• 分子量: 411.435
• InChiKey: BHMPYLKJONSOOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.28
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  [2-[Bromo-(4-methylphenyl)sulfonylmethyl]phenyl]methyl-trimethylsilane 在 四丁基氟化铵 作用下， 以 乙腈 为溶剂， 反应 0.67h， 以27%的产率得到3',4'-dihydro-1'-(p-tolylsulfonyl)-6-[(p-tolylsulfonyl)methylene]spiro[2,4-cyclohexadiene-1,2'-(1'H)-naphthalene]
  参考文献：
  名称：

  Chemistry of Conversions of [o-[1-Halo-1-(p-tolylsulfonyl)alkyl]benzyl]trimethylsilanes to o-Quinodimethanes and Benzocyclobutenes

  摘要：

  Trimethyl[o-[bromo(p-tolylsulfonyl)methyl]benyzl]silane (10) is prepared from o-[(trimethylsilyl)methyl]benzyl p-tolyl sulfone (9), n-BuLi, and bromine. Sulfone 9 eliminates trimethylsilyl bromide upon reaction with TBAF in acetonitrile to give the presumed intermediate, alpha-sulfonyl-o-quinodimethane 11, which (1) dimerizes to disulfone 12 and (2) is trapped by alkyl fumarates to yield (p-tolylsulfonyl)tetrahydronaphthalenes 17a,b and 18a,b, respectively. Sulfone 9 is converted by n-BuLi and alkyl halides to alpha-alkyl-alpha-bromosulfones 19a-f which react with TBAF to give alpha-sulfonylbenzocyclobutenes 21a-f and vinyl sulfones 23a-f, apparently upon ring closure and upon 1,5-sigmatropic rearrangements of hydrogen in alpha-sulfonyl-o-quinodimethane intermediates 20a-f and 22a-f. Further, sulfone 9, n-BuLi, and tert-butyl hypochlorite yield alpha-chlorosulfone 26 and alpha,alpha-dichlorosulfone 27. TBAF effects dechlorotrimethylsilation of 27 to chloro(p-tolylsulfonyl)cyclobutene 28 presumably upon formation and cyclization of o-quinodimethane 29. Silanes 10, 19a-f, and 27 are therefore practical synthons for o-quinodimethane intermediates 11, 20a-f and 22a-f, and 29 respectively.

  DOI：

  10.1021/jo9705935
• 作为产物：
  描述：

  Trimethyl-[[2-[(4-methylphenyl)sulfonylmethyl]phenyl]methyl]silane 在 正丁基锂 、 溴 作用下， 生成 [2-[Bromo-(4-methylphenyl)sulfonylmethyl]phenyl]methyl-trimethylsilane
  参考文献：
  名称：

  Chemistry of Conversions of [o-[1-Halo-1-(p-tolylsulfonyl)alkyl]benzyl]trimethylsilanes to o-Quinodimethanes and Benzocyclobutenes

  摘要：

  Trimethyl[o-[bromo(p-tolylsulfonyl)methyl]benyzl]silane (10) is prepared from o-[(trimethylsilyl)methyl]benzyl p-tolyl sulfone (9), n-BuLi, and bromine. Sulfone 9 eliminates trimethylsilyl bromide upon reaction with TBAF in acetonitrile to give the presumed intermediate, alpha-sulfonyl-o-quinodimethane 11, which (1) dimerizes to disulfone 12 and (2) is trapped by alkyl fumarates to yield (p-tolylsulfonyl)tetrahydronaphthalenes 17a,b and 18a,b, respectively. Sulfone 9 is converted by n-BuLi and alkyl halides to alpha-alkyl-alpha-bromosulfones 19a-f which react with TBAF to give alpha-sulfonylbenzocyclobutenes 21a-f and vinyl sulfones 23a-f, apparently upon ring closure and upon 1,5-sigmatropic rearrangements of hydrogen in alpha-sulfonyl-o-quinodimethane intermediates 20a-f and 22a-f. Further, sulfone 9, n-BuLi, and tert-butyl hypochlorite yield alpha-chlorosulfone 26 and alpha,alpha-dichlorosulfone 27. TBAF effects dechlorotrimethylsilation of 27 to chloro(p-tolylsulfonyl)cyclobutene 28 presumably upon formation and cyclization of o-quinodimethane 29. Silanes 10, 19a-f, and 27 are therefore practical synthons for o-quinodimethane intermediates 11, 20a-f and 22a-f, and 29 respectively.

  DOI：

  10.1021/jo9705935

文献信息

• Chemistry of Conversions of [<i>o</i>-[1-Halo-1-(<i>p</i>-tolylsulfonyl)alkyl]benzyl]trimethylsilanes to <i>o</i>-Quinodimethanes and Benzocyclobutenes
  作者：Brian D. Lenihan、Harold Shechter

  DOI：10.1021/jo9705935

  日期：1998.4.1

  Trimethyl[o-[bromo(p-tolylsulfonyl)methyl]benyzl]silane (10) is prepared from o-[(trimethylsilyl)methyl]benzyl p-tolyl sulfone (9), n-BuLi, and bromine. Sulfone 9 eliminates trimethylsilyl bromide upon reaction with TBAF in acetonitrile to give the presumed intermediate, alpha-sulfonyl-o-quinodimethane 11, which (1) dimerizes to disulfone 12 and (2) is trapped by alkyl fumarates to yield (p-tolylsulfonyl)tetrahydronaphthalenes 17a,b and 18a,b, respectively. Sulfone 9 is converted by n-BuLi and alkyl halides to alpha-alkyl-alpha-bromosulfones 19a-f which react with TBAF to give alpha-sulfonylbenzocyclobutenes 21a-f and vinyl sulfones 23a-f, apparently upon ring closure and upon 1,5-sigmatropic rearrangements of hydrogen in alpha-sulfonyl-o-quinodimethane intermediates 20a-f and 22a-f. Further, sulfone 9, n-BuLi, and tert-butyl hypochlorite yield alpha-chlorosulfone 26 and alpha,alpha-dichlorosulfone 27. TBAF effects dechlorotrimethylsilation of 27 to chloro(p-tolylsulfonyl)cyclobutene 28 presumably upon formation and cyclization of o-quinodimethane 29. Silanes 10, 19a-f, and 27 are therefore practical synthons for o-quinodimethane intermediates 11, 20a-f and 22a-f, and 29 respectively.