spiro-1'(3'H)-one | 113446-65-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: spiro-1'(3'H)-one
• 英文别名: spiro[3H-indene-2,7'-bicyclo[4.2.0]octa-1,3,5-triene]-1-one
• CAS: 113446-65-4
• 化学式: C₁₆H₁₂O
• 分子量: 220.271
• InChiKey: LDDWFJDEWAJQRN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  1,1'-epoxy-(E)-1,1'-bi(benzocyclobutenylidene) 以 氯仿 为溶剂， 反应 336.0h， 以40%的产率得到spiro-1'(3'H)-one
  参考文献：
  名称：

  Photosensitized oxidation of 1,1'-bi[benzocyclobutenylidene]

  摘要：

  In an attempt to explore whether singlet molecular oxygen reactions could be used to obtain access to antiaromatic species, we carried out the Rose Bengal photosensitized oxygenation of (E)- and (Z)-1,1'-bi(benzocyclobutenylidene) (7-E and 7-Z). The photooxidation resulted in a facile E/Z isomerization accompanied by the sluggish uptake of oxygen and formation of benzocyclobutenone 8, spiroindanone 9, phthalide 10, and dione 11. We found no evidence, however, for the generation of the corresponding benzocyclobutadiene via a O-1(2)-ene reaction. On the contrary, the data suggests that the isomerization of the diaryl olefin can occur in the absence of sensitizer, while product formation is a free radical autoxidative process, presumably initiated by the interaction of excited dye with molecular oxygen (''type IIc''). The formation of 8-11 may be rationalized in terms of secondary rearrangements (unzipping and cyclization) of the initially formed polyperoxide or polyperoxy radical. The absence of singlet oxygen ene product may reflect the increased activation energy required to generate an antiaromatic product. Alternatively, the inability of the ring methylene hydrogens to attain a pseudoaxial conformation may actually be the controlling factor in inhibiting the ene process.

  DOI：

  10.1021/jo00066a017

文献信息

• Barton, John W.; Shepherd, Michael K., Journal of the Chemical Society. Perkin transactions I, 1987, p. 1561 - 1566
  作者：Barton, John W.、Shepherd, Michael K.

  DOI：——

  日期：——
• BARTON, JOHN W.;SHEPHERD, MICHAEL K., J. CHEM. SOC. PERKIN TRANS.,(1987) N 7, 1561-1565
  作者：BARTON, JOHN W.、SHEPHERD, MICHAEL K.

  DOI：——

  日期：——
• Photosensitized oxidation of 1,1'-bi[benzocyclobutenylidene]
  作者：Aryeh A. Frimer、Joseph Weiss

  DOI：10.1021/jo00066a017

  日期：1993.7

  In an attempt to explore whether singlet molecular oxygen reactions could be used to obtain access to antiaromatic species, we carried out the Rose Bengal photosensitized oxygenation of (E)- and (Z)-1,1'-bi(benzocyclobutenylidene) (7-E and 7-Z). The photooxidation resulted in a facile E/Z isomerization accompanied by the sluggish uptake of oxygen and formation of benzocyclobutenone 8, spiroindanone 9, phthalide 10, and dione 11. We found no evidence, however, for the generation of the corresponding benzocyclobutadiene via a O-1(2)-ene reaction. On the contrary, the data suggests that the isomerization of the diaryl olefin can occur in the absence of sensitizer, while product formation is a free radical autoxidative process, presumably initiated by the interaction of excited dye with molecular oxygen (''type IIc''). The formation of 8-11 may be rationalized in terms of secondary rearrangements (unzipping and cyclization) of the initially formed polyperoxide or polyperoxy radical. The absence of singlet oxygen ene product may reflect the increased activation energy required to generate an antiaromatic product. Alternatively, the inability of the ring methylene hydrogens to attain a pseudoaxial conformation may actually be the controlling factor in inhibiting the ene process.