1,3-Ditert-butyl-5-[2-[3-[2-(3,5-ditert-butylphenyl)ethynyl]-5-ethynylphenyl]ethynyl]benzene | 189286-70-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 1,3-Ditert-butyl-5-[2-[3-[2-(3,5-ditert-butylphenyl)ethynyl]-5-ethynylphenyl]ethynyl]benzene
• CAS: 189286-70-2
• 化学式: C₄₀H₄₆
• 分子量: 526.805
• InChiKey: MRUDELTWZPGLNA-UHFFFAOYSA-N

物化性质

• 沸点：
  614.1±55.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.9
• 重原子数：
  40
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,3,5-三溴苯 、 1,3-Ditert-butyl-5-[2-[3-[2-(3,5-ditert-butylphenyl)ethynyl]-5-ethynylphenyl]ethynyl]benzene 在 copper(l) iodide 、 TEA 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以73%的产率得到benzene<3-1,3,5>:5-ethynyl-1,3-phenylene:5-ethynyl-1,3-di-tert-butylbenzene
  参考文献：
  名称：

  Phenylacetylene Dendrimers by the Divergent, Convergent, and Double-Stage Convergent Methods

  摘要：

  The divergent, convergent, and double-stage convergent methods for synthesizing phenylacetylene dendritic macromolecules are examined. Syntheses based on the divergent or double-stage convergent approaches are severely hampered by poor solubility of the growing macromolecules. The double-stage method is nonetheless successfully used in attaining a high molecular weight and apparently monodisperse dendrimer. Using the convergent approach, high molecular weight mono- and tridendrons are prepared. The repetitive chemistry employed for monodendron preparation includes palladium-catalyzed coupling of terminal acetylenes to an aromatic dibromide containing a trimethylsilyl (TMS) masked terminal acetylene. The synthetic cycle is completed by removing the TMS group under mildly basic conditions. These monodendrons can be coupled around a trifunctional core, such as triiodobenzene, yielding tridendrons. Solubility of both the mono- and the tridendrons is strongly dependent on the nature of the peripheral group. Qualitatively, solubility tends to plummet in the early stages of growth. Provided that growth can be sustained, however, this trend tends to reverse as the synthesis progresses. The best peripheral group of those examined thus far for maintaining adequate solubility of both mono- and tridendrons over this critical solubility minimum is di-tert-butylphenylacetylene. For dendrimers containing this peripheral group, solubility is high even in aliphatic hydrocarbon solvents at room temperature. When poor solubility does not hamper the synthesis, the limiting factors to sustaining growth become as much dependent on the ability to purify and characterize the product of the coupling reaction as on the chemistry of the coupling reaction itself. Size-exlusion chromatography is shown to be inadequate for differentiating partially coupled products from fully coupled tridendrons. This problem is believed to be especially severe for stiff dendritic macromolecules, since their molecular cross section is essentially constant once two of the three monodendrons have coupled to the central core. Unequivocal proof of structure for mono- and tridendrons through generation four (C1134H1146, mol wt 14 776) has been obtained using a combination of chromatographic techniques, isotope labeling studies, mass spectrometry, and multidimensional NMR experiments.

  DOI：

  10.1021/ja00090a002
• 作为产物：
  描述：

  1,3-di-tert-butyl-5-ethynylbenzene 在 氢氧化钾 、 copper(l) iodide 、 TEA 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 1,3-Ditert-butyl-5-[2-[3-[2-(3,5-ditert-butylphenyl)ethynyl]-5-ethynylphenyl]ethynyl]benzene
  参考文献：
  名称：

  Phenylacetylene Dendrimers by the Divergent, Convergent, and Double-Stage Convergent Methods

  摘要：

  The divergent, convergent, and double-stage convergent methods for synthesizing phenylacetylene dendritic macromolecules are examined. Syntheses based on the divergent or double-stage convergent approaches are severely hampered by poor solubility of the growing macromolecules. The double-stage method is nonetheless successfully used in attaining a high molecular weight and apparently monodisperse dendrimer. Using the convergent approach, high molecular weight mono- and tridendrons are prepared. The repetitive chemistry employed for monodendron preparation includes palladium-catalyzed coupling of terminal acetylenes to an aromatic dibromide containing a trimethylsilyl (TMS) masked terminal acetylene. The synthetic cycle is completed by removing the TMS group under mildly basic conditions. These monodendrons can be coupled around a trifunctional core, such as triiodobenzene, yielding tridendrons. Solubility of both the mono- and the tridendrons is strongly dependent on the nature of the peripheral group. Qualitatively, solubility tends to plummet in the early stages of growth. Provided that growth can be sustained, however, this trend tends to reverse as the synthesis progresses. The best peripheral group of those examined thus far for maintaining adequate solubility of both mono- and tridendrons over this critical solubility minimum is di-tert-butylphenylacetylene. For dendrimers containing this peripheral group, solubility is high even in aliphatic hydrocarbon solvents at room temperature. When poor solubility does not hamper the synthesis, the limiting factors to sustaining growth become as much dependent on the ability to purify and characterize the product of the coupling reaction as on the chemistry of the coupling reaction itself. Size-exlusion chromatography is shown to be inadequate for differentiating partially coupled products from fully coupled tridendrons. This problem is believed to be especially severe for stiff dendritic macromolecules, since their molecular cross section is essentially constant once two of the three monodendrons have coupled to the central core. Unequivocal proof of structure for mono- and tridendrons through generation four (C1134H1146, mol wt 14 776) has been obtained using a combination of chromatographic techniques, isotope labeling studies, mass spectrometry, and multidimensional NMR experiments.

  DOI：

  10.1021/ja00090a002

文献信息

• Photoswitchable Flexible and Shape-Persistent Dendrimers:  Comparison of the Interplay between a Photochromic Azobenzene Core and Dendrimer Structure
  作者：Li-Xin Liao、Francesco Stellacci、Dominic V. McGrath

  DOI：10.1021/ja036418p

  日期：2004.2.1

  Two analogous classes of dendrimers with a single azobenzene moiety at the core have been prepared. Flexible benzyl aryl ether dendrimers 1a-e were obtained in good yields by direct alkylation of diphenolic azobenzene 3 with benzyl aryl ether dendrons [G-n]-Br (n = 0-4). In rigid dendrimers 2a-e, the azobenzene configurational switch was linked to phenylacetylene dendrons through acetylenic linkages

  已经制备了两类类似的在核心具有单个偶氮苯部分的树枝状聚合物。通过二酚偶氮苯 3 与苄基芳基醚树枝状化合物 [Gn]-Br (n = 0-4) 的直接烷基化，以良好的收率获得了柔性苄基芳基醚树枝状聚合物 1a-e。在刚性树枝状聚合物 2a-e 中，偶氮苯构型开关通过炔键连接到苯乙炔树枝状聚合物上，以保持这些树枝状聚合物的形状持久性。这两种不同类别的树枝状大分子与偶氮苯核的比较揭示了树枝状结合后光致变色部分的性质的差异以及树枝状大分子性质的光调制的显着差异。E--> Z 光异构化量子产率随着树枝状大分子 1a-e 的生成量增加而显着降低，但树枝状大分子 2a-e 仅略微降低。然而，增加生成并没有显着改变热异构化动力学或激活障碍。当偶氮苯单元受到辐照时，含偶氮苯树枝状聚合物 2b-e 的流体力学体积受到显着调节，而树枝状聚合物 1b-e 的流体力学体积仅受到轻微影响。
• Structurally Rigid and Optically Active Dendrimers
  作者：Qiao-Sheng Hu、Vincent Pugh、Michal Sabat、Lin Pu

  DOI：10.1021/jo990856q

  日期：1999.10.1

  Novel rigid and optically active dendrimers containing cross-conjugated units are synthesized from the coupling of phenylacetylene-based dendrons with an optically pure diacetate of 4,4',6,6'-tetrabromo-1, 1'-bi-2-naphthol. The UV and fluorescence spectroscopic studies demonstrate that there is a very efficient energy migration from the cross-conjugated dendrons to the center core, leading to greatly enhanced fluorescences at higher generations. This is the first example of an efficient energy migration conducted in an optically pure dendritic system, which is potentially useful in developing an enantioselective fluorescence sensor. The generation 2 dendrimer has been used to catalyze the asymmetric reaction of diethylzinc with aldehydes and has shown high enantioselectivity in the presence of Ti(O-i-Pr)(4).
• Xu Zhifu, Kahr Michael, Walker Kathleen L., Wilkins Charles L., Moore Jef+, J. Amer. Chem. Soc, 116 (1994) N 11, S 4537-4550
  作者：Xu Zhifu, Kahr Michael, Walker Kathleen L., Wilkins Charles L., Moore Jef+

  DOI：——

  日期：——