Trimethyl-{2-[2-methyl-1-(toluene-4-sulfonyl)-propyl]-benzyl}-silane | 160929-79-3

• 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: Trimethyl-{2-[2-methyl-1-(toluene-4-sulfonyl)-propyl]-benzyl}-silane
• CAS: 160929-79-3
• 化学式: C₂₁H₃₀O₂SSi
• 分子量: 374.62
• InChiKey: MLECAJWRLFSXQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  25.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  Trimethyl-{2-[2-methyl-1-(toluene-4-sulfonyl)-propyl]-benzyl}-silane 在 六甲基磷酰三胺 、 正丁基锂 、 四丁基氟化铵 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Synthesis and Conversions of Substituted o-[(Trimethylsilyl)methyl]benzyl p-Tolyl Sulfones to o-Quinodimethanes and Products Thereof

  摘要：

  Use of o-[(trimethylsilyl)methyl]benzyl p-tolyl sulfone (3) for synthesis and cycloaddition of substituted o-quinodimethanes has been investigated. Sulfone 3 is prepared from 2-methylbenzyl alcohol (4) by reactions with n-BuLi and chlorotrimethylsilane to form o-[(trimethylsilyl)methyl]benzyl alcohol (7) which phosphorus tribromide converts to o-[(trimethylsilyl)methyl]benzyl bromide (8). Displacement of 8 with sodium p-toluenesulfinate yields 3. Sulfone 3 is alkylated at its alpha-sulfonyl position upon deprotonation with n-BuLi followed by methyl iodide, ethyl, butyl, allyl, and benzyl bromides, and 5-bromo-1-pentene, respectively. Acylations occur using acid chlorides. Dialkylation occurs upon further reaction with n-BuLi and an alkyl halide. 1,4-Eliminations of alpha,alpha-dialkyl sulfones 11 with tetrabutylammonium fluoride (TBAF) give alpha,alpha-dialkyl-o-quinodimethanes (29); 3 is therefore a synthon for the o-quinadimethane-alpha,alpha-dianion (34). o-Quinodimethanes 29 undergo (1) cycloaddition with acrylonitrile, acrylate esters, and alkyl fumarates to yield 1,1-disubstituted-tetrahydronaphthalenes (30) and (2) 1,5-sigmatropic rearrangements of hydrogen to give styrenes (32). The stereochemistries of the various cycloadditions reveal significant mechanism information.

  DOI：

  10.1021/jo970592c
• 作为产物：
  描述：

  2-[(trimethylsilyl)methyl]benzyl alcohol 在 六甲基磷酰三胺 、 正丁基锂 、 三溴化磷 作用下， 以 四氢呋喃 为溶剂， 生成 Trimethyl-{2-[2-methyl-1-(toluene-4-sulfonyl)-propyl]-benzyl}-silane
  参考文献：
  名称：

  取代的邻[[（三甲基甲硅烷基）甲基]苄基对甲苯砜：用于制备邻喹啉甲烷环加成物的实用试剂

  摘要：

  已经开发了合成和将甲硅烷基砜1，4-消除为邻喹啉甲烷的有效方法。

  DOI：

  10.1016/s0040-4039(00)78329-8

文献信息

• Substituted o-[(Trimethylsilyl)methyl]benzyl p-tolyl sulfones: Practical reagents for preparing cycloadducts of o-quinodimethanes
  作者：Brian D. Lenihan、Harold Shechter

  DOI：10.1016/s0040-4039(00)78329-8

  日期：1994.10

  Effective methods for synthesis and 1,4-elimination of silyl sulfones to o-quinodimethanes have been developed.

  已经开发了合成和将甲硅烷基砜1，4-消除为邻喹啉甲烷的有效方法。
• 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.
• Synthesis and Conversions of Substituted <i>o</i>-[(Trimethylsilyl)methyl]benzyl <i>p</i>-Tolyl Sulfones to <i>o</i>-Quinodimethanes and Products Thereof
  作者：Brian D. Lenihan、Harold Shechter

  DOI：10.1021/jo970592c

  日期：1998.4.1

  Use of o-[(trimethylsilyl)methyl]benzyl p-tolyl sulfone (3) for synthesis and cycloaddition of substituted o-quinodimethanes has been investigated. Sulfone 3 is prepared from 2-methylbenzyl alcohol (4) by reactions with n-BuLi and chlorotrimethylsilane to form o-[(trimethylsilyl)methyl]benzyl alcohol (7) which phosphorus tribromide converts to o-[(trimethylsilyl)methyl]benzyl bromide (8). Displacement of 8 with sodium p-toluenesulfinate yields 3. Sulfone 3 is alkylated at its alpha-sulfonyl position upon deprotonation with n-BuLi followed by methyl iodide, ethyl, butyl, allyl, and benzyl bromides, and 5-bromo-1-pentene, respectively. Acylations occur using acid chlorides. Dialkylation occurs upon further reaction with n-BuLi and an alkyl halide. 1,4-Eliminations of alpha,alpha-dialkyl sulfones 11 with tetrabutylammonium fluoride (TBAF) give alpha,alpha-dialkyl-o-quinodimethanes (29); 3 is therefore a synthon for the o-quinadimethane-alpha,alpha-dianion (34). o-Quinodimethanes 29 undergo (1) cycloaddition with acrylonitrile, acrylate esters, and alkyl fumarates to yield 1,1-disubstituted-tetrahydronaphthalenes (30) and (2) 1,5-sigmatropic rearrangements of hydrogen to give styrenes (32). The stereochemistries of the various cycloadditions reveal significant mechanism information.