1-(2,2-Dimethyl-propyl)-3-(2,2,2-trifluoro-1-trifluoromethyl-ethoxy)-cyclohexa-1,4-diene | 145428-38-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(2,2-Dimethyl-propyl)-3-(2,2,2-trifluoro-1-trifluoromethyl-ethoxy)-cyclohexa-1,4-diene
• 英文别名: 1,4-Cyclohexadiene, 1-(2,2-dimethylpropyl)-3-[2,2,2-trifluoro-1-(trifluoromethyl)ethoxy]-；1-(2,2-dimethylpropyl)-3-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)cyclohexa-1,4-diene
• CAS: 145428-38-2
• 化学式: C₁₄H₁₈F₆O
• 分子量: 316.287
• InChiKey: VVLJOZRNYVNWPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  六氟异丙醇 、 (2,2-二甲基丙基)苯 生成 1-(2,2-Dimethyl-propyl)-3-(2,2,2-trifluoro-1-trifluoromethyl-ethoxy)-cyclohexa-1,4-diene
  参考文献：
  名称：

  Photochemistry of 2,3-dimethyl-2,3-diphenylbutane: carbon-carbon homolysis and protonation-induced side-chain fragmentation

  摘要：

  In dichloromethane upon 248-nm (or 254-nm) irradiation, 2,3-dimethyl-2,3-diphenylbutane (bicumene) undergoes homolysis of the central C-C bond to yield two alpha,alpha-dimethylbenzyl (cumyl) radicals (PHI(hom) = 0.18). In 2,2,2-trifluoroethanol (TFE), this reaction is less efficient (PHI(hom) < 0.02), but a new process is observed, i.e., biphotonic ionization followed by C-C fragmentation of the resulting radical cation leading to the cumyl radical and the cumyl cation. The latter reacts with TFE to give cumyl trifluoroethyl ether. In the more acidic solvent 1,1,1,3,3,3-hexafluoroisopropyl alcohol, the electronically excited state of bicumene is efficiently protonated by the solvent to yield a cyclohexadienyl-type carbocation which undergoes side-chain fragmentation to produce cumyl cation, which was directly observed by its UV absorption and whose electrophilic reactivity was characterized. Photoprotonation followed by side-chain fragmentation was also observed with beta-phenylalkanols which give rise to the aliphatic oxo compounds derived from the beta-carbon of the side chain.

  DOI：

  10.1021/j100205a049

文献信息

• Photochemistry of 2,3-dimethyl-2,3-diphenylbutane: carbon-carbon homolysis and protonation-induced side-chain fragmentation
  作者：Joaquim L. Faria、Steen Steenken

  DOI：10.1021/j100205a049

  日期：1992.12

  In dichloromethane upon 248-nm (or 254-nm) irradiation, 2,3-dimethyl-2,3-diphenylbutane (bicumene) undergoes homolysis of the central C-C bond to yield two alpha,alpha-dimethylbenzyl (cumyl) radicals (PHI(hom) = 0.18). In 2,2,2-trifluoroethanol (TFE), this reaction is less efficient (PHI(hom) < 0.02), but a new process is observed, i.e., biphotonic ionization followed by C-C fragmentation of the resulting radical cation leading to the cumyl radical and the cumyl cation. The latter reacts with TFE to give cumyl trifluoroethyl ether. In the more acidic solvent 1,1,1,3,3,3-hexafluoroisopropyl alcohol, the electronically excited state of bicumene is efficiently protonated by the solvent to yield a cyclohexadienyl-type carbocation which undergoes side-chain fragmentation to produce cumyl cation, which was directly observed by its UV absorption and whose electrophilic reactivity was characterized. Photoprotonation followed by side-chain fragmentation was also observed with beta-phenylalkanols which give rise to the aliphatic oxo compounds derived from the beta-carbon of the side chain.