5,7-Di-tert-butyl-2-methyl-spiro[2.5]octa-4,7-dien-6-on | 17207-15-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 5,7-Di-tert-butyl-2-methyl-spiro[2.5]octa-4,7-dien-6-on
• 英文别名: 5,7-Ditert-butyl-2-methylspiro[2.5]octa-4,7-dien-6-one
• CAS: 17207-15-7
• 化学式: C₁₇H₂₆O
• 分子量: 246.393
• InChiKey: FRDWUHOFFVDXOT-UHFFFAOYSA-N

物化性质

• 沸点：
  333.4±32.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  甲醇 、 5,7-Di-tert-butyl-2-methyl-spiro[2.5]octa-4,7-dien-6-on 在 nickel dichloride 作用下， 反应 1.0h， 以75%的产率得到4-(2'-methoxypropyl)-2,6-di-tert-butylphenol
  参考文献：
  名称：

  Sviridov, B. D.; Porkhun, V. I., Journal of general chemistry of the USSR, 1988, vol. 58, # 7, p. 1385 - 1388

  摘要：

  DOI：

文献信息

• Radical Ion Probes. 8. Direct and Indirect Electrochemistry of 5,7-Di-<i>tert</i>-butylspiro[2.5]octa-4,7-dien-6-one and Derivatives
  作者：J. Paige Phillips、Jason G. Gillmore、Phillip Schwartz、Larry E. Brammer、Daniel J. Berger、J. M. Tanko

  DOI：10.1021/ja972795o

  日期：1998.1.1

  (stable) distonic radical anion. The direct electrochemistry of these compounds is characterized by rate limiting electron transfer (with α ≈ 0.5), suggesting that while ring opening is extremely rapid, the radical anions do have a discrete lifetime (i.e., electron transfer and ring opening are not concerted). Utilizing homogeneous redox catalysis, rate constants for electron transfer between 1a, 1b,

  5,7-二叔丁基螺[2.5]octa-4,7-dien-6-one (1a), 1-methyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (1a), 1-methyl-5,7-di-tert-butylspiro[2.5] 的直接和间接电化学结果2.5]octa-4,7-dien-6-one (1b) 和 1,1,-dimethyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (1c ) 报道。产物分析表明，所有这些底物的还原都会导致环丙烷开环产物；开环以适度的选择性发生，导致更多取代（稳定）的异张力自由基阴离子。这些化合物的直接电化学的特点是电子转移限速（α≈0.5），这表明虽然开环非常快，但自由基阴离子确实具有离散的寿命（即电子转移和开环不协调）。利用均相氧化还原催化，1a、1b、1b
• Radical Ion Probes. 7. Behavior of a “Hypersensitive” Probe for Single Electron Transfer in Reactions <i>Not</i> Involving Electron Transfer
  作者：James M. Tanko、Larry E. Brammer

  DOI：10.1021/jo970584w

  日期：1997.8.1

  1-Methyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (8) and 1,1-dimethyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (1) react with thiophenoxide ion to produce cyclopropane ring-opened products. Thermodynamic considerations effectively rule out any possibility that single electron transfer is involved in theses reactions; the process PhS- + substrate --> PhS. + substrate(.-) is endothermic by over 50 kcal/mol! Nucleophilic attack occurs both at the least- and most-hindered carbons of the cyclopropyl group, and the product ratio (R(1 degrees/2 degrees) from 8 and R(1 degrees/3 degrees) from 1, where 1 degrees, 2 degrees, and 3 degrees refer to the regioisomeric phenyl sulfides formed from these substrates) is found to vary with solvent. In dipolar, aprotic solvents, nucleophilic attack occurs preferentially at the least-hindered carbon of the cyclopropyl group (R(1 degrees/2 degrees) and R(1 degrees/3 degrees) approximate to 4-5), consistent with an S(N)2 mechanism. In protic solvents, products arising from nucleophilic attack at the more-substituted carbon of the cyclopropyl group become increasingly important, consistent with the onset of a carbocationic (S(N)2(C+)) pathway. The strengths and weaknesses of 1 and 8 as probes for single electron transfer are discussed in the context of these results.