3,3,6,6-Tetrakis(2-methoxyphenyl)-1,2-dioxane | 93584-74-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 3,3,6,6-Tetrakis(2-methoxyphenyl)-1,2-dioxane
• 英文别名: 3,3,6,6-Tetrakis(2-methoxyphenyl)dioxane
• CAS: 93584-74-8
• 化学式: C₃₂H₃₂O₆
• 分子量: 512.602
• InChiKey: RHUUDQIODUBSFG-UHFFFAOYSA-N

物化性质

• 沸点：
  638.4±55.0 °C(Predicted)
• 密度：
  1.169±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1,1-双(邻甲氧基苯基)乙烯 以85%的产率得到
  参考文献：
  名称：

  GOLLNICK, K.;SCHNATTERER, A., TETRAHEDRON LETT., 1984, 25, N 26, 2735-2738

  摘要：

  DOI：

文献信息

• Formation of 1,2-dioxanes by electron-transfer photooxygenation of 1,1-disubstituted ethylenes
  作者：Klaus Gollnick、Albert Schnatterer

  DOI：10.1016/s0040-4039(01)81277-6

  日期：——

  (3a–e) in high yields (>907%) when subjected to electron-transfer photooxygenation in the presence of DCA. Whereas 1,1-diphenyl-ethylene (1f) and 1,1-di(p-chlorophenyl)ethylene (1h) yield the 1,2-dioxanes 3f and 3h at 30% and less than 10%, respectively, there is negligible (if any) 1,2-dioxane formation with 1,1-di(m-anisyl)ethylene (1i). 1,2-Dioxane formation proceeds in a chain reaction (Scheme 1). N-Vinylcarbazol

  富电子的1,1-二芳基乙烯（1a–e）在经过电子转移光氧合后，可以以高收率（> 907％）提供3,3,6,6-四芳基-1,2-二恶烷（3a–e）。 DCA的存在。1,1,1-二苯基乙烯（1f）和1,1-二（对氯苯基）乙烯（1h）分别产生30％和小于10％的1,2-二恶烷3f和3h，可忽略不计（如果有的话）与1,1-二（间茴香基）乙烯（1i）形成1,2-二恶烷。1,2-二恶烷的形成在链式反应中进行（方案1）。但是，N-乙烯基咔唑（1g）通过环丁烷衍生物7生成1,2-二恶烷3g（方案2）。
• Substituent-dependent electron-transfer-induced photooxygenation of 1,1-diarylethylenes
  作者：Klaus Gollnick、Albert Schnatterer、Gerald Utschick

  DOI：10.1021/jo00074a035

  日期：1993.10

  Rates and products of 9,10-dicyanoanthracene-sensitized photooxygenations of 1,1-diarylethylenes (1a-r) in acetonitrile were studied. If at least one of the aryl groups carries an electron-donating substituent at the para (or ortho) position (1a-1), 3,3,6,6-tetraaryl-1,2-dioxanes (2a-1) are generated in high yields (85-100%). Benzophenones (3) are the only other observable products. 1,1-Diphenylethylene (1n) and its m-methoxy (1m), p-chloro (1q,p), and p-nitro (1q,r) derivatives,however, yield mainly benzophenones (3m-r) (>50%) (the p-nitro compounds only in the presence of biphenyl). 1,2-Dioxanes (2m-p), cyclobutanes (4n-p), and alpha-tetralones (5m-o) are obtained as side products. Dioxanes, benzophenones, and alpha-tetralones are products of electron-transfer induced oxygenations involving triplet ground-state molecular oxygen, O-3(2). Singlet molecular oxygen, O2(1DELTA(g)),contributes to the benzophenone formation from strongly electron-donor substituted diarylethylenes. An exception is the most powerful electron-donor substituted diarylethylene 1a, with which O2(1DELTA(g)) undergoes an electron-transfer reaction affording dioxane 2a. Dioxane formation proceeds via free-radical cations 1.+, which enter into a chain reaction with 1, O-3(2), and another molecule of 1 to yield dioxane 2 and a new radical cation 1.+ that maintains the chain reaction. The efficiency of this chain process, however, is found to be several orders of magnitude smaller than expected. To explain this result, a 1,6-biradical.1-1-O2.is proposed to be generated in this chain reaction as the product-determining intermediate that predominantly fragments into O-3(2) and two molecules of 1. Cyclization to dioxane 2 and transformation to benzophenone 3 occur at presumably less than 0.1% from this biradical. The pathways leading to cyclobutanes (4) and alpha-tetralones (5) are also discussed.