4,5-Di-tert-butyl-6-oxa-2-thia-bicyclo[3.1.0]hex-3-ene 2,2-dioxide | 134132-40-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 4,5-Di-tert-butyl-6-oxa-2-thia-bicyclo[3.1.0]hex-3-ene 2,2-dioxide
• 英文别名: 4,5-ditert-butyl-6-oxa-2λ6-thiabicyclo[3.1.0]hex-3-ene 2,2-dioxide
• CAS: 134132-40-4
• 化学式: C₁₂H₂₀O₃S
• 分子量: 244.355
• InChiKey: HKOFKQLKAXWOAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  46.67
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4,5-Di-tert-butyl-6-oxa-2-thia-bicyclo[3.1.0]hex-3-ene 2,2-dioxide 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以18%的产率得到3,4-Di-tert-butylfuran
  参考文献：
  名称：

  Oxidation of 3,4-di-tert-butylthiophene 1,1-dioxide

  摘要：

  The oxidation of 3,4-di-tert-butylthiophene 1,1-dioxide (4) by a variety of reagents under various conditions was investigated in detail. Oxidation of 4 with peracids (MCPBA, trifluoroperacetic acid) affords the thiete 1,1-dioxide 6 and the sulfone 7, both in moderate yield. The formation of these compounds can be explained as being the result of an acid-catalyzed rearrangement of the initial product, epoxy sulfone 5 via the carbocation 8. Under basic conditions the rearrangement is suppressed and thus 5 can be isolated in good yield. Treatment of 5 with BF3.Et2O affords 6 and the sultine 10. Oxidation of 4 with alkaline H2O2 involves a smooth Michael addition of HOO- to give the hydroperoxide 17 in high yield. This represents the first example of the formation of an isolable beta-hydroperoxy sulfone, a species which has been hypothesized to be an intermediate in the formation of epoxy sulfones by the oxidation of alpha,beta-unsaturated sulfones with alkaline H2O2. Thermal decomposition of 17 affords the ketone 19 quantitatively. Reduction of 17 with NaBH4 gives the alcohol 20. On treatment with base, both 17 and 20 undergo ring opening to yield the alkene 18 in good yield.

  DOI：

  10.1021/jo00012a037
• 作为产物：
  描述：

  3,4-di-t-butylthiophene 1,1-dioxide 在 sodium carbonate 、 间氯过氧苯甲酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 4.0h， 以77%的产率得到4,5-Di-tert-butyl-6-oxa-2-thia-bicyclo[3.1.0]hex-3-ene 2,2-dioxide
  参考文献：
  名称：

  Oxidation of 3,4-di-tert-butylthiophene 1,1-dioxide

  摘要：

  The oxidation of 3,4-di-tert-butylthiophene 1,1-dioxide (4) by a variety of reagents under various conditions was investigated in detail. Oxidation of 4 with peracids (MCPBA, trifluoroperacetic acid) affords the thiete 1,1-dioxide 6 and the sulfone 7, both in moderate yield. The formation of these compounds can be explained as being the result of an acid-catalyzed rearrangement of the initial product, epoxy sulfone 5 via the carbocation 8. Under basic conditions the rearrangement is suppressed and thus 5 can be isolated in good yield. Treatment of 5 with BF3.Et2O affords 6 and the sultine 10. Oxidation of 4 with alkaline H2O2 involves a smooth Michael addition of HOO- to give the hydroperoxide 17 in high yield. This represents the first example of the formation of an isolable beta-hydroperoxy sulfone, a species which has been hypothesized to be an intermediate in the formation of epoxy sulfones by the oxidation of alpha,beta-unsaturated sulfones with alkaline H2O2. Thermal decomposition of 17 affords the ketone 19 quantitatively. Reduction of 17 with NaBH4 gives the alcohol 20. On treatment with base, both 17 and 20 undergo ring opening to yield the alkene 18 in good yield.

  DOI：

  10.1021/jo00012a037

文献信息

• Oxidation of congested thiophene 1,1-dioxides with m-chloroperbenzoic acid. Formation of epoxides vs. ring-contracted thiete 1,1-dioxides
  作者：Juzo Nakayama、Hiroaki Kamiyama

  DOI：10.1016/s0040-4039(00)60818-3

  日期：——

  Highly congested thiophene 1,1-dioxides, which carry two bulky substituents at 3- and 4-positions, afford the corresponding epoxides in high yields on oxidation with m-chloroperbenzoic acid in the presence of sodium carbonate, while the oxidation in the absence of sodium carbonate gives the ring-contracted thiete 1,1-dioxides as the principal product.

  高度拥塞噻吩1,1-二氧化物，其携带在3-两个大体积的取代基和4-位，得到在氧化高产率与相应的环氧化物米在碳酸钠的存在下氯过苯甲酸，同时在不存在的氧化碳酸钠得到的主要产物是缩环的1,1-二氧化物。
• NAKAYAMA, J.;SUGIHARA, Y., J. ORG. CHEM., 56,(1991) N2, C. 4001-4005
  作者：NAKAYAMA, J.、SUGIHARA, Y.

  DOI：——

  日期：——