3,4-Di-tert-butyl-1,1-dioxo-2,3-dihydro-1H-1λ⁶-thiophen-3-ol | 134132-50-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢噻吩类
• 英文名称: 3,4-Di-tert-butyl-1,1-dioxo-2,3-dihydro-1H-1λ⁶-thiophen-3-ol
• 英文别名: 3,4-ditert-butyl-1,1-dioxo-2H-thiophen-3-ol
• CAS: 134132-50-6
• 化学式: C₁₂H₂₂O₃S
• 分子量: 246.371
• InChiKey: ZTYWLLMPFMRSAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  54.37
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3,4-Di-tert-butyl-1,1-dioxo-2,3-dihydro-1H-1λ⁶-thiophen-3-ol 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 7.0h， 以100%的产率得到4-[1-Methanesulfonyl-meth-(Z)-ylidene]-2,2,5,5-tetramethyl-hexan-3-one
  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 hydroxide 、 sodium tetrahydroborate 、 双氧水 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 8.0h， 生成 3,4-Di-tert-butyl-1,1-dioxo-2,3-dihydro-1H-1λ⁶-thiophen-3-ol
  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

• NAKAYAMA, J.;SUGIHARA, Y., J. ORG. CHEM., 56,(1991) N2, C. 4001-4005
  作者：NAKAYAMA, J.、SUGIHARA, Y.

  DOI：——

  日期：——