3,3,6,6-Tetrakis<4-(N-dimethylamino)phenyl>-1,2-dioxane | 93584-77-1

• 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-(N-dimethylamino)phenyl>-1,2-dioxane
• 英文别名: 3,3,6,6-tetrakis(4-dimethylamino-phenyl)-1,2-dioxane；N,N-dimethyl-4-[3,6,6-tris[4-(dimethylamino)phenyl]dioxan-3-yl]aniline
• CAS: 93584-77-1
• 化学式: C₃₆H₄₄N₄O₂
• 分子量: 564.771
• InChiKey: LSRJNZYXNLQKKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4,4-亚乙烯双(N,N-二甲基苯胺) 在 氧气 、 2,6,9,10-tetracyanoanthracene 作用下， 以 乙腈 为溶剂， 反应 0.67h， 生成 3,3,6,6-Tetrakis<4-(N-dimethylamino)phenyl>-1,2-dioxane
  参考文献：
  名称：

  1,1-二芳基乙烯的光化学电子转移反应

  摘要：

  已经研究了由光激发的氰基蒽诱导的 1,1-二芳基乙烯 (1) 的二聚化、亲核加成和氧化反应。1,1-二苯基乙烯 (1a) 产生 2 + 2 和 2 + 4 环二聚体和一个脱氢二聚体，而 1,1-二苯甲基乙烯 (1b) 产生两个脱氢二聚体和 1,1-双（4-（二甲氨基）苯基）乙烯（ 1c) 不形成二聚体。脱氢二聚体的形成伴随着氰基蒽敏化剂的还原。对于 1b 的二聚化，可以通过添加醌来改变量子产率和产物比率。然后氢醌取代还原的敏化剂。甲醇亲核加成到 1a/sup.+/ 的反应常数为 1.6 x 10/sup 9/ M/sup -1/s/sup -1/；除了 1b/sup .+/ 它大约是 10/sup 7/ M/sup -1/s/sup -1/。甲醇不能有效地添加到 1c/sup 中。+ / 。二芳基乙烯的光氧化作用主要在链式过程中产生相应的 3,3,6,6-四芳基-1,2-二恶烷。在甲醇和氧气存在下，1a

  DOI：

  10.1021/ja00283a034

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

  DOI：——

  日期：——