4-bromo-16-carboxaldehyde-[2.2]paracyclophane | 320749-00-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-bromo-16-carboxaldehyde-[2.2]paracyclophane
• 英文别名: (±)-4-bromo-16-formyl[2.2]paracyclophane；4-formyl-12-bromo[2.2]paracyclophane；11-Bromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene-5-carbaldehyde；11-bromotricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene-5-carbaldehyde
• CAS: 320749-00-6
• 化学式: C₁₇H₁₅BrO
• 分子量: 315.209
• InChiKey: PDEKZHFJFSKVGD-UHFFFAOYSA-N

物化性质

• 熔点：
  180-189 °C (decomp)(Solvent: Hexane)
• 沸点：
  433.2±45.0 °C(Predicted)
• 密度：
  1.374±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-bromo-16-carboxaldehyde-[2.2]paracyclophane 在 四(三苯基膦)钯 、 四丁基溴化铵 、 palladium diacetate 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Blending Through-Space and Through-Bond π–π-Coupling in [2,2′]-Paracyclophane-oligophenylenevinylene Molecular Wires

  摘要：

  A series of ZnP-pCp-oPPV-C-60 conjugates covalently connected through [2,2']-paracyclophane-oligophenylenevinylene (pCp-oPPV) bridges containing one, two, and three [2,2']-paracyclophanes (pCps) has been prepared in multistep synthetic procedures involving Horner-Wadsworth-Emmons olefination reactions and/or Heck type Pd-catalyzed reactions. Molecular modeling suggests that charge transfer is effectively mediated by the pCp-oPPVs through a predominant hole-transfer mechanism. Photophysical investigation supports molecular modeling and reveals two major trends. On one hand, C-60 excitation of 1, 2, and 3 leads exclusively to charge transfer between pCp and C-60 to afford a ZnP-(pCp-oPPV)(circle+)-C-60(circle-) radical ion pair state without giving rise to a subsequent charge shift to yield the ZnP circle+-pCp-oPPV-C-60(circle-) radical ion pair state. On the other hand, ZnP excitation of 1, 2, and 3 results in a rather slow charge transfer between ZnP and C-60, after which the ZnP circle+-pCp-oPPV-C-60(circle-) radical ion pair state evolves. In temperature-dependent ZnP fluorescence experiments, which were performed in the temperature range from 273 to 338 K, two domains are discernible: low and high temperature behaviors. In the low temperature range (i.e., below 30 degrees C) the rate constants do not change, suggesting that a superexchange mechanism is the modus operandi. In the high temperature range (i.e., >30 degrees C) the rate constants increase. Moreover, we find rather strong distance dependence for 1 and 2 and weak distance dependence for 2 and 3. A damping factor of 0.145 angstrom(-1) is derived for the former pair and 0.012 angstrom(-1) for the latter.

  DOI：

  10.1021/ja401239r
• 作为产物：
  描述：

  对二甲苯二聚体 在 正丁基锂 、 溴 作用下， 以 四氢呋喃 、 四氯化碳 、 正己烷 为溶剂， 反应 6.0h， 生成 4-bromo-16-carboxaldehyde-[2.2]paracyclophane
  参考文献：
  名称：

  基于芳基[2.2]对环环烷的手性区域异构体的水杨醛类似物：苯氧基亚胺配体构建的新来源。

  摘要：

  高效，高产率的两种新型区域异构水杨醛类似物，4-甲酰基-13-（2-羟基苯基）-[2.2]对环环糊精和4-甲酰基-12-（2-羟基苯基）-[2.2]对环环糊精（iso ‐FHPhPC和伪‐FHPhPC描述了分别基于芳基[2.2]对环环烷骨架构建的。骨架形成的关键阶段是对环烷酰基卤化物与芳基硼酸的Suzuki交叉偶联。阐述了通过席夫碱与α-苯乙胺对映体将外消旋羟基醛拆分为对映异构体的有效方法，并根据非对映异构亚胺的X射线分析建立了对映体的绝对构型。从这些手性羟基醛开始，获得了属于芳基[2.2]对环环烷族的双齿，三齿和四齿苯氧基亚胺配体的第一个代表。在Et 2 Zn与醛的不对称加成中测试了配体的诱导能力。

  DOI：

  10.1002/ijch.201100096

文献信息

• Synthesis of planar chiral [2.2]paracyclophane-based amino thioureas and their application in asymmetric aldol reactions of ketones with isatins
  作者：Yu Lu、Yudao Ma、Shaobo Yang、Manyuan Ma、Hongju Chu、Chun Song

  DOI：10.1016/j.tetasy.2013.07.023

  日期：2013.9

  were used as bifunctional catalysts for organocatalytic enantioselective aldol reactions between ketones and isatins, affording the desired adducts containing a chiral tertiary alcohol in high yields (up to 92% yield) and with good enantioselectivity (up to 88% ee). This is a successful example of employing planar chiral [2.2]paracyclophane-based amino thioureas in asymmetric aldol reactions.

  已经设计并合成了几种新颖的基于[2.2]对环环烷的氨基硫脲。[2.2]对环烷基氨基硫脲被用作双官能催化剂，用于酮和靛红之间的有机催化对映选择性醛醇缩合反应，以高收率（高达92％的收率）和良好的对映选择性（最高收率）提供了所需的含有手性叔醇的加合物。 88％ee）。这是在不对称醛醇缩合反应中使用基于平面手性[2.2]对环硫基的氨基硫脲的成功实例。
• Synthesis and photophysical studies of through-space conjugated [2.2]paracyclophane-based naphthalene fluorophores
  作者：E. Benedetti、M.-L. Delcourt、B. Gatin-Fraudet、S. Turcaud、L. Micouin

  DOI：10.1039/c7ra10038h

  日期：——

  straightforward method for the synthesis of a new class of small organic fluorophores bearing both [2.2]paracyclophane and naphthalene subunits using an intramolecular dehydrogenative Diels–Alder reaction as a key step. These compounds are characterized by a compact three-dimensional structure as well as through-space conjugated push–pull systems, and possess interesting spectroscopic characteristics that may be

  在这项工作中，我们报告了一种简单的方法，该方法使用分子内脱氢Diels-Alder反应作为关键步骤来合成同时带有[2.2]对环环烷和萘亚基的新型小型有机荧光团。这些化合物的特点是具有紧凑的三维结构以及贯穿空间的共轭推挽系统，并具有有趣的光谱特性，这些特性可能对创新化学探针和光学传感器的开发有用。
• Highly Enantioselective Asymmetric Transfer Hydrogenation: A Practical and Scalable Method To Efficiently Access Planar Chiral [2.2]Paracyclophanes
  作者：Marie-Léonie Delcourt、Simon Felder、Serge Turcaud、Corina H. Pollok、Christian Merten、Laurent Micouin、Erica Benedetti

  DOI：10.1021/acs.joc.9b00372

  日期：2019.5.3

  (ATH) to control the planar chirality of a range of substituted [2.2]paracyclophanes (pCps). Our strategy enabled us to perform both the kinetic resolution (KR) of racemic compounds and the desymmetrization of centrosymmetric meso derivatives on synthetically useful scales. High selectivities (up to 99% ee) and good yields (up to 48% for the KRs and 74% for the desymmetrization reactions) could be observed

  我们在此报告了一种基于不对称转移氢化（ATH）来控制一系列取代的[2.2]对环环烷（pCps）的平面手性的通用实用方法。我们的策略使我们能够在合成上有用的尺度上执行外消旋化合物的动力学拆分（KR）和中心对称的内消旋衍生物的去对称化。对于几种多取代的对环环烷，包括一系列含溴分子，可以观察到高选择性（高达99％ee）和良好的产率（KR高达48％，脱对称反应高达74％）。优化的工艺可以运行至克级，而不会降低反应效率。由于其广泛的适用性，ATH方法似乎是获取对映纯形式的平面手性pCps的选择方法。
• Planar Chiral Analogues of PRODAN Based on a [2.2]Paracyclophane Scaffold: Synthesis and Photophysical Studies
  作者：Simon Felder、Marie-Léonie Delcourt、Manon H. E. Bousquet、Denis Jacquemin、Rafael Rodríguez、Ludovic Favereau、Jeanne Crassous、Laurent Micouin、Erica Benedetti

  DOI：10.1021/acs.joc.1c02071

  日期：2022.1.7

  We describe the synthesis and photophysical characterization of differently substituted planar chiral analogues of PRODAN based on a [2.2]paracyclophane scaffold. This experimental and theoretical study highlights that the (chir)optical properties of the new “phane” compounds, which incorporate an electron-withdrawing propionyl moiety and an electron-donating dimethylamino group at their para or pseudo-para

  我们描述了基于 [2.2] 对环芳烃支架的不同取代的 PRODAN 平面手性类似物的合成和光物理表征。这项实验和理论研究强调了新的“ phane ”化合物的（手性）光学性质，在它们的对位或伪对位上包含一个吸电子丙酰基部分和一个供电子二甲氨基，很大程度上取决于它们的取代模式。特别是，对于这一系列分子，当两个取代基以非“共面”排列的方式放置在 pCp 核心的两个环上时，观察到更明显的溶剂致变色和清晰的手性行为（pseudo-para衍生物）。这一观察结果可能有助于设计具有微调光物理特性的新型基于 pCp 的发光体。
• Through-Space Charge Transfer and Nonlinear Optical Properties of Substituted Paracyclophane
  作者：Joseph Zyss、Isabelle Ledoux、Sergei Volkov、Vladimir Chernyak、Shaul Mukamel、Glenn P. Bartholomew、Guillermo C. Bazan

  DOI：10.1021/ja0022526

  日期：2000.12.1

  The introduction, within a pi -conjugated donor-acceptor molecule, of an intermediate barrier to electron tunneling and ifs size scaling and influence on,electronic polarization properties have remained so far elusive issues of great potential interest toward the fine-tuning of the linear and nonlinear optical properties of molecular materials. Paracyclophane (pCP) provides a most relevant cornerstone for more elaborate compounds where donor and acceptor substituents are made to interact through a sterically constrained pi-pi stack. A first attempt in this direction is reported here with the synthesis of a model dipolar 4-(4-dihexylaminostyryl)-16-(4-nitrostyryl)[2.2]paracyclophane and the subsequent experimental and theoretical study of its quadratic nonlinear optical properties. A major outcome of this investigation is the evidence of a significant "through-space" charge transfer as unambiguously designated by the strong departure of the beta quadratic hyperpolarizability tensor of the full doubly substituted molecule (60 x 10(-30) esu) from the additive beta value (18 x 10(-30) esu) expected for strictly noninteracting singly substituted pCP moieties, This desired increase of nonlinear efficiency upon substitution is not offset by the usual red-shift of the absorption spectrum which generally curtails application perspectives in more common uninterrupted conjugated chains. The collective nonlinear polarization behavior involving the full end-to-end molecular structure is confirmed by theoretical calculations using the Collective Electron Oscillator (CEO) approach which furthermore indicates a significantly enhanced role of electron-hole pair delocalization in the higher order nonlinear response, compared to the linear polarizability or the static dipole moment.