3,3,6,6-Tetrakis(4-methylphenyl)-1,2-dioxane | 68313-23-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,3,6,6-Tetrakis(4-methylphenyl)-1,2-dioxane
• 英文别名: 3,3,6,6-tetra(p-methylphenyl)-1,2-dioxane；3,3,6,6-Tetrakis(4-methylphenyl)dioxane
• CAS: 68313-23-5
• 化学式: C₃₂H₃₂O₂
• 分子量: 448.605
• InChiKey: ZNPZHWYKAQYYRB-UHFFFAOYSA-N

物化性质

• 熔点：
  222-223.5 °C
• 沸点：
  564.2±50.0 °C(Predicted)
• 密度：
  1.101±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  34
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3,6,6-Tetrakis(4-methylphenyl)-1,2-dioxane 反应 5.0h， 以42%的产率得到4,4'-二甲基二苯甲酮
  参考文献：
  名称：

  通过CO键裂解的1,6-二自由基中间体对3,3,6,6-四（对甲氧基苯基）-1,2-二恶烷的新型光裂解

  摘要：

  研究了3,3,6,6-四芳基-1,2-二恶烷的光解和热解。3,3,6,6-四（对甲氧基苯基）-1,2-二恶烷的光解通过新型反应得到1,4,4-三（对甲氧基苯基）-3-丁烯-1-酮和对甲氧基苯酚C ＝ O键裂解了1，6-二自由基中间体，而热解主要通过O ＝ O键裂解了1，6-二氧基二自由基中间体而提供了预期的分解产物4，4′-二甲氧基二苯甲酮。

  DOI：

  10.1016/0040-4039(96)01855-2
• 作为产物：
  描述：

  1,1-二(对甲苯)乙烯 以82%的产率得到
  参考文献：
  名称：

  HAYNES R. K.; PROBERT M. K. S.; WILMOT I. D., AUSTRAL. J. CHEM., 1978, 31, NO 8, 1737-1746

  摘要：

  DOI：

文献信息

• Photoreactivities of Contact Charge-Transfer Complexes between 1,1-Diarylethenes and Oxygen Molecules. Dimerization and Oxygenation Accelerated in Medium Polar Solvent
  作者：Masanobu Kojima、Akito Ishida、Setsuo Takamuku

  DOI：10.1246/bcsj.71.2211

  日期：1998.9

  studied in terms of the effects of the solvent polarity, additives, substituents on the aromatic rings, and the excitation wavelength on the product distribution, as well as in terms of the result of the photolysis of 2. On the basis of these results, it was shown that 2 was produced through dimer cation radicals of 1, whereas 3 was formed through the photolysis of 2 and the autoxidation of 1 initiated by

  1,1-二芳基乙烯的接触电荷转移 (CCT) 带的选择性激发 [Ar = 4-MeOC6H4 (1a); 4-MeC6H4 (1b)；Ph (1c)] 与 CH2Cl2 和 MeCN 中的分子氧导致形成相应的 3,3,6,6-四芳基-1,2-二恶烷 (2) 作为主要产物，以及二芳基酮 (3)。从溶剂极性、添加剂、芳环上的取代基、激发波长对产物分布的影响以及产物分布的影响，研究了制备2和3的反应机理和中间体。 2 的光解。根据这些结果，表明 2 是通过 1 的二聚阳离子自由基产生的，而 3 是通过 2 的光解和由中性自由基引发的 1 的自氧化形成的，它一定是由 1 (1•+) 的单体阳离子自由基与超氧阴离子自由基反应生成的。特别是2的形成在很大程度上取决于溶剂极性...
• Photooxygenation of 1,1-Diarylethylenes via Addition of Oxygen to the 1,4-Dimer Radical Cations, Catalyzed by 10-Methylacridinium Ion
  作者：Morifumi Fujita、Akira Shindo、Akito Ishida、Tetsuro Majima、Setsuo Takamuku、Shunichi Fukuzumi

  DOI：10.1246/bcsj.69.743

  日期：1996.3

  Photooxygenation of 1,1-diarylethylene occurs efficiently using 10-methylacridinium ion as a photocatalyst to yield the 1,2-dioxane and/or the diaryl ketone depending on the substituents on the ary...

  1,1-二芳基乙烯的光氧化反应使用 10-甲基吖啶鎓离子作为光催化剂有效地发生，根据芳基上的取代基产生 1,2-二恶烷和/或二芳基酮。
• Mechanism of Photochemical Reaction of Contact Charge Transfer Pair between 1,1-Diarylethene and Oxygen
  作者：Masanobu Kojima、Akito Ishida、Setsuo Takamuku

  DOI：10.1246/cl.1993.979

  日期：1993.6

  Selective excitation of the contact charge transfer band between 1,1-diarylethene and oxygen in dichloromethane and acetonitrile gave 3,3,6,6-tetraaryl-1,2-dioxane and benzophenone derivative through an electron transfer reaction. The proposed mechanism was confirmed by the direct observation of the dimer cation radical of the olefin trapped by a triplet oxygen in pulse radiolysis.

  1,1-二芳基乙烯和氧气在二氯甲烷和乙腈中的接触电荷转移带的选择性激发通过电子转移反应得到3,3,6,6-四芳基-1,2-二恶烷和二苯甲酮衍生物。通过在脉冲辐解中被三线态氧捕获的烯烃的二聚阳离子自由基的直接观察证实了所提出的机制。
• 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.
• Haynes,R.K. et al., Australian Journal of Chemistry, 1978, vol. 31, p. 1737 - 1746
  作者：Haynes,R.K. et al.

  DOI：——

  日期：——