1,12-dioxa[12](1,4)naphthalenophane | 1221497-25-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,12-dioxa[12](1,4)naphthalenophane
• CAS: 1221497-25-1
• 化学式: C₂₀H₂₆O₂
• 分子量: 298.425
• InChiKey: JNYZBUAQPYWJNA-UHFFFAOYSA-N

物化性质

• 熔点：
  77 °C
• 沸点：
  450.7±15.0 °C(Predicted)
• 密度：
  1.013±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.73
• 重原子数：
  22.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,12-dioxa[12](1,4)naphthalenophane 在 仲丁基锂 、 鹰爪豆碱 、 碘 作用下， 以 乙醚 、 正己烷 、 环己烷 为溶剂， 以82%的产率得到21-Iodo-2,13-dioxatricyclo[12.6.2.015,20]docosa-1(21),14(22),15,17,19-pentaene
  参考文献：
  名称：

  Enantioselective Synthesis of Planar-Chiral 1,n-Dioxa[n]paracyclophanes via Catalytic Asymmetric ortho-Lithiation

  摘要：

  Highly enantioselective ortho-lithiation and dilithiation of 1,n-dioxa[n]paracyclophanes were realized with the use of see-butyllithium and a catalytic or stoichiometric amount of sparteine. Quenching with various electrophiles, such as iodine, iodomethane, and chlorodiphenylphosphine, afforded chiral mono- and disubstituted paracyclophanes with good to excellent ee.

  DOI：

  10.1021/ol100444u
• 作为产物：
  描述：

  1,4-二羟基萘 、 1,10-二溴癸烷 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以40%的产率得到1,12-dioxa[12](1,4)naphthalenophane
  参考文献：
  名称：

  Enantioselective Synthesis of Planar-Chiral 1,n-Dioxa[n]paracyclophanes via Catalytic Asymmetric ortho-Lithiation

  摘要：

  Highly enantioselective ortho-lithiation and dilithiation of 1,n-dioxa[n]paracyclophanes were realized with the use of see-butyllithium and a catalytic or stoichiometric amount of sparteine. Quenching with various electrophiles, such as iodine, iodomethane, and chlorodiphenylphosphine, afforded chiral mono- and disubstituted paracyclophanes with good to excellent ee.

  DOI：

  10.1021/ol100444u

文献信息

• Dioxacyclophanes as a Scaffold for Silicon-based Circularly Polarized Luminescent Materials
  作者：Yoshinori Yamanoi、Tsukasa Usuki、Kenichiro Omoto、Masaki Shimada、Hikaru Koike、Munetaka Iwamura、Koichi Nozaki、Daisuke Saito、Masako Kato、Hiroshi Nishihara

  DOI：10.1016/j.tetlet.2019.03.033

  日期：2019.4

  compounds (−)-(R)-1, (+)-(R)-2, and (−)-(R)-3 were prepared by (+)-sparteine-mediated aryl metalation and an electrophilic reaction with chlorosilanes. The absolute configurations of the planar chirality were determined in the R form by single-crystal X-ray analysis. Optically active compound (+)-(R)-2 exhibited blue fluorescence and a CPL signal with a dissymmetry factor (glum value) of 0.001 in solution

  设计并合成了平面手性二氧杂环烷，作为具有圆偏振发光（CPL）材料的关键支架。代表性的平面手性1,12-二氧杂[12]（1,4）萘酞菁衍生的有机硅烷化合物（-）-（R）-1，（+）-（R）-2和（-）-（R）-通过（+）-天冬氨酸介导的芳基金属化和与氯硅烷的亲电反应制备3个。通过单晶X射线分析以R形式确定平面手性的绝对构型。旋光性化合物（+）-（R）-2呈现蓝色荧光，并且CPL信号具有不对称因子（克LUM 0.001在溶液中的值）。通过DFT和TD-DFT计算证实了所观察到的光谱性质，从而证实了电子结构。
• Asymmetric ortho-lithiation of 1,n-dioxa[n]paracyclophane derivatives for the generation of planar chirality
  作者：Kazumasa Kanda、Risa Hamanaka、Kohei Endo、Takanori Shibata

  DOI：10.1016/j.tet.2011.12.031

  日期：2012.2

  The asymmetric induction of planar chirality in 1,n-dioxa[n]paracyclophane derivatives via asymmetric ortho-lithiation is described. Enantioselective ortho-lithiation of unflippable 1,n-dioxa[n]paracyclophanes (n <= 11) using sec-BuLi-(-)-sparteine at -78 degrees C and subsequent treatment with electrophiles gave the corresponding planar-chiral monosubstituted paracyclophanes with excellent ee. Further lithiation of these compounds and treatment with electrophiles gave planar-chiral paracyclophanes with two different substituents. Dilithiation of unflippable 1,n-dioxa[n]paracyclophanes gave the corresponding C(2)symmetrical disubstituted products with almost perfect ee. In the case of flippable 1,n-dioxa[n]paracyclophanes (n >= 12), a stepwise reaction was required for the highly enantioselective formation of disubstituted products. (C) 2011 Elsevier Ltd. All rights reserved.