tetramethylthiophene S-oxide | 178875-13-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: tetramethylthiophene S-oxide
• 英文别名: 2,3,4,5-Tetramethylthiophene-oxide；2,3,4,5-tetramethylthiophene 1-oxide
• CAS: 178875-13-3
• 化学式: C₈H₁₂OS
• 分子量: 156.249
• InChiKey: QJNHCBWJVXBGFZ-UHFFFAOYSA-N

物化性质

• 熔点：
  122-124 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  299.2±13.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 4-oxo-4-phenylbut-2-ynoate 、 tetramethylthiophene S-oxide 以 苯 为溶剂， 反应 10.0h， 以83%的产率得到methyl 2-benzoyl-3,4,5,6-tetramethylbenzoate
  参考文献：
  名称：

  噻吩S-氧化物环加成至丙二烯，炔和苯炔

  摘要：

  噻吩已经与在存在炔处理米氯过氧酸，得到取代的芳烃如cycloadducts。另外，噻吩S-氧化物是通过从噻吩氧化制得的，并在随后的步骤中与炔烃进行环加成反应。反应的结果取决于噻吩S-氧化物的空间需求。某些噻吩S-氧化物可以在高达140 °C的温度下反应而不会分解。噻吩作为脱氧产物是主要的副产物。噻吩S-氧化物与丙二烯的反应部分产生12a型噻双环[2.2.1]庚烯S-氧化物和13以及加香的产品。噻吩S-氧化物也环加成苯并。

  DOI：

  10.1039/b303091c
• 作为产物：
  描述：

  2,3,4,5-四甲基噻吩 在 三氟化硼乙醚 、 间氯过氧苯甲酸 作用下， 生成 tetramethylthiophene S-oxide
  参考文献：
  名称：

  从噻吩S-氧化物到 7-噻二环[2.2.1]庚-5-烯

  摘要：

  具有 7-硫双环 [2.2.1]hept-5-ene 单元的低聚环已通过噻吩 S-氧化物与烯烃的环加成反应立体选择性制备，随后用 PBr3 对环加合物的磺氧基桥进行脱氧。

  DOI：

  10.3184/030823409x12562932030738

文献信息

• Lewis Acid Catalysis in the Oxidative Cycloaddition of Thiophenes¹
  作者：Yuanqiang Li、Thies Thiemann、Tsuyoshi Sawada、Shuntaro Mataka、Masashi Tashiro

  DOI：10.1021/jo961985z

  日期：1997.11.1

  Thiophenes 1 were treated with m-chloroperbenzoic acid (m-CPBA) under BF3 . Et2O catalysis to afford thiophene S-monoxides. These could be reacted in situ as intermediary species with a number of dienophiles to provide arenes (with alkynes as dienophiles) or 7-thiabicyclo[2.2.1]hept-2-ene 7-oxides (with alkenes as dienophiles). It was also possible to isolate thiophene S-monoxides in solution and to cycloadd them in a second step. In either way it could be shown that the use of BF3 . Et2O enhances the yields of the oxidative cycloaddition of thiophenes considerably. Moreover a greater variety of dienophiles (29a, 29b, 29c) could be reacted with thiophenes than in the case of the noncatalyzed reaction. All cycloadditions catalyzed by BF3 . Et2O give only a single diastereoisomer as cycloadduct. The reactions show a high pi-facial selectivity, a fact that can be explained by the Cieplak-effect. Without added dienophiles, 2-methylthiophene (le) gave a single dimer (36) of 2-methylthiophene S-monoxide, whereas 2,5-dimethylthiophene (la) gave three dimers (32a-c). In the case of tetrasubstituted thiophenes, thiophene S-monoxides (e.g., 31b and 31c) could be isolated in substance.
• Cycloaddition of thiophene S-oxides to allenes, alkynes and to benzyne
  作者：Thies Thiemann、Hideki Fujii、Daisuke Ohira、Kazuya Arima、Yuanqiang Li、Shuntaro Mataka

  DOI：10.1039/b303091c

  日期：——

  the presence of m-chloroperoxybenzoic acid to give substituted arenes as cycloadducts. Alternatively, thiophene S-oxides have been prepared by oxidation from thiophenes and have been subjected to cycloaddition with alkynes in a subsequent step. The outcome of the reaction is dependent on the steric demand of the thiophene S-oxide. Some thiophene S-oxides can be reacted at temperatures as high as 140°C

  噻吩已经与在存在炔处理米氯过氧酸，得到取代的芳烃如cycloadducts。另外，噻吩S-氧化物是通过从噻吩氧化制得的，并在随后的步骤中与炔烃进行环加成反应。反应的结果取决于噻吩S-氧化物的空间需求。某些噻吩S-氧化物可以在高达140 °C的温度下反应而不会分解。噻吩作为脱氧产物是主要的副产物。噻吩S-氧化物与丙二烯的反应部分产生12a型噻双环[2.2.1]庚烯S-氧化物和13以及加香的产品。噻吩S-氧化物也环加成苯并。
• From thiophene <i>S</i>-oxides to 7-thiabicyclo[2.2.1]hept-5-enes
  作者：Yuan-Qiang Li、Carolin Thiemann、Daisuke Ohira、Shuntaro Mataka、Masashi Tashiro、Thies Thiemann

  DOI：10.3184/030823409x12562932030738

  日期：2009.11

  Oligocycles with a 7-thiabicyclo[2.2.1]hept-5-ene unit have been prepared stereoselectively by cycloaddition of thiophene S-oxides to alkenes and subsequent deoxygenation of the sulfoxy bridge of the cycloadducts with PBr3.

  具有 7-硫双环 [2.2.1]hept-5-ene 单元的低聚环已通过噻吩 S-氧化物与烯烃的环加成反应立体选择性制备，随后用 PBr3 对环加合物的磺氧基桥进行脱氧。