6,6-dimethyldibenzofulvene oxide | 81277-93-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 6,6-dimethyldibenzofulvene oxide
• 英文别名: 3',3'-Dimethylspiro[fluorene-9,2'-oxirane]
• CAS: 81277-93-2
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: ALRWILMXSCBXBF-UHFFFAOYSA-N

物化性质

• 熔点：
  92-93 °C(Solv: ethanol (64-17-5); water (7732-18-5))
• 沸点：
  357.2±11.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6,6-dimethyldibenzofulvene oxide 生成 9-acetyl-9-methylfluorene
  参考文献：
  名称：

  Photochemistry of the carbonyl ylide produced by reaction of fluorenylidene with acetone. A comparison of carbonyl and nitrile ylides

  摘要：

  DOI：

  10.1021/ja00310a090
• 作为产物：
  描述：

  9-isopropylidene-9H-fluorene 在 potassium sulfate 、 potassium hydrogensulfate 、 oxone 、 碳酸氢钠 、 丙酮 作用下， 以 水 为溶剂， 反应 1.0h， 以85%的产率得到6,6-dimethyldibenzofulvene oxide
  参考文献：
  名称：

  Reaktivit�t und Selektivit�t bei der Oxidation von Styrolderivaten. IV. Untersuchungen zur Oxidation von substituierten ?,?-Dimethylstyrolen

  摘要：

  The liquid phase oxidation of substituted (p-MeO-, p-Cl-, m-CF3-) 2-aryl-3-methyl-but-2-enes, of 1,1-diphenyl-2-methyl-propene, of 1-ethoxy-2-methyl-1-phenyl-propene and of 9-isopropylidene-fluorene with pure oxygen was investigated in chlorobenzene solution and in presence of cumene and of cumene hydroperoxide in the temperature range 65-125 degrees C. The product yields were determined gaschromatographically. The differences of the activation energies of epoxide formation and the parallel reactions were calculated. They amount to 19-48 kJ/mol. The epoxide selectivity increases with increasing temperature and increasing concentration of olefin. The relative chain propagation constants (k(pC=C)) were determined by competitive oxidation with cumene. The k(pC=C) values of substituted beta,beta-dimethylstyrenes can be correlated by a LFE-relationship with the ionisation energies of the olefins.

  DOI：

  10.1002/prac.19983400308

文献信息

• Different<i>Z</i>/<i>E</i>-Selectivity Depending upon the Length of the Acyl Side Chain in the Formation of 2,2′-Diacyl-9,9′-bifluorenylidene
  作者：Atsushi Oota、Toshinobu Imai、Ayumi Yamazaki、Toru Oba、Michinori Karikomi、Masahiro Minabe

  DOI：10.1246/bcsj.79.333

  日期：2006.2

  We studied the formation of 2,2′-diacyl-9,9′-bifluorenylidene from 2-acyl-9-bromofluorene via the corresponding intermediate 9-bromo-9,9′-bifluorenyl. It was found that dehydrobromination of the 9-bromo-9,9′-bifluorenyl derivatives occurred through the E2 elimination sequence, suggesting that the configuration of 9-bromo-9,9′-bifluorenyl isomers determined the stereochemistry of the product. Facile isomerization of the formed 9,9′-bifluorenylidenes may give the observed stereo-selectivity depending upon the length of the acyl side chain.

  我们研究了 2-酰基-9-溴芴通过相应的中间体 9-溴-9,9′-二芴形成 2,2′-二酰基-9,9′-二芴的过程。研究发现，9-溴-9,9′-二芴基衍生物的脱氢溴化作用是通过 E2 消除顺序进行的，这表明 9-溴-9,9′-二芴基异构体的构型决定了产物的立体化学性质。根据酰基侧链的长度，所形成的 9,9′-二芴基异构体可能会产生观察到的立体选择性。
• A kinetic study of the reactions of carbonyl ylides formed by the addition of fluorenylidene to ketones
  作者：P. C. Wong、D. Griller、J. C. Scaiano

  DOI：10.1021/ja00388a026

  日期：1982.12
• Electrochemical studies of the reduction of 6,6-dimethyldibenzofulvene oxide and tetraphenyloxirane
  作者：C. Nuntnarumit、W. Edward Null、M. Dale Hawley

  DOI：10.1021/jo00199a016

  日期：1984.12