[(4,5-dimethoxybenzene-1,2-diyl)diethyne-2,1-diyl]bis(trimethylsilane) | 803733-65-5

• 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: [(4,5-dimethoxybenzene-1,2-diyl)diethyne-2,1-diyl]bis(trimethylsilane)
• 英文别名: 2-[4,5-dimethoxy-2-(2-trimethylsilylethynyl)phenyl]ethynyl-trimethylsilane
• CAS: 803733-65-5
• 化学式: C₁₈H₂₆O₂Si₂
• 分子量: 330.574
• InChiKey: KDDPEWYNTZCKDP-UHFFFAOYSA-N

物化性质

• 熔点：
  88 °C
• 沸点：
  367.4±42.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  [(4,5-dimethoxybenzene-1,2-diyl)diethyne-2,1-diyl]bis(trimethylsilane) 在 [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]gold bis(trifluoromethanesulfonyl)imidate 、 水 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 9.75h， 生成 5,6-dimethoxyindene
  参考文献：
  名称：

  均相金催化中的CO挤出：通过水与金亚乙烯基的加成反应生成的金酰基物种的反应性

  摘要：

  在这里，我们描述了一种新的金催化的脱羰茚合成。二炔底物的协同σ，π-活化作用可生成亚乙烯基金中间体，该中间体在加水后可转化为酰基金，这是迄今为止几乎没有报道的一种有机金化合物。后者被证明经历了CO的挤出，这是均相金催化完全未知的基本步骤。通过调节起始二炔系统的电子和位阻性质，可以利用这种新的反应性以高收率合成茚衍生物。

  DOI：

  10.1002/anie.201409859
• 作为产物：
  描述：

  邻苯二甲醚 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 碘 、 过碘酸 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 21.0h， 生成 [(4,5-dimethoxybenzene-1,2-diyl)diethyne-2,1-diyl]bis(trimethylsilane)
  参考文献：
  名称：

  Halogen Bonding of (Iodoethynyl)benzene Derivatives in Solution

  摘要：

  Halogen bonding (XB) between (iodoethynyl)benzene donors and quinuclidine in benzene affords binding free enthalpies (ΔG, 298 K) between -1.1 and -2.4 kcal mol(-1), with a strong LFER with the Hammett parameter σpara. The enthalpic driving force is compensated by an unfavorable entropic term. The binding affinity of XB acceptors increases in the order pyridine < C═O < S═O < P═O < quinuclidine. Diverse XB packing motifs are observed in the solid state.

  DOI：

  10.1021/ol502099j

文献信息

• Grignard Reagent/CuI/LiCl-Mediated Stereoselective Cascade Addition/Cyclization of Diynes: A Novel Pathway for the Construction of 1-Methyleneindene Derivatives
  作者：De-Yao Li、Yin Wei、Min Shi

  DOI：10.1002/chem.201302191

  日期：2013.11.11

  Diynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1‐methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through

  含有环丙烷基团的二炔顺利进行新型分子内和立体选择性级联加成/环化反应，以中等至良好的收率生产相应的1-亚甲基茚衍生物。这种有趣的转化是由格氏试剂/ CuI在温和条件下用LiCl作为添加剂介导的。所获得的产物可以通过环丙基开环容易地进一步官能化。在氘标记和对照实验的基础上，还提出了合理的反应机理。
• The trisubstituted-triazole approach to extended functional naphthalocyanines
  作者：Michal Juríček、Kathleen Stout、Paul H.J. Kouwer、Alan E. Rowan

  DOI：10.1142/s1088424611003781

  日期：2011.9

  Recently, a novel modular approach to octatriazole-derived phthalocyanines (Pcs; 1) was developed and optimized in our group; herein, the pool of the functional Pc materials was expanded for an additional candidate (2), a fused derivative of 1. Compared with 1, the aromaticity in 2 is extended by an additional four benzene and eight triazole rings and, in addition, the triazole units and the Pc core co-create four functional, in-plane cavities. Various methods to link the unsubstituted carbon atoms of the neighboring triazoles in 1 to afford atomically flat naphthalocyanine (Nc) analogs (2), containing eight fused triazole moieties, were studied. Several synthetic routes were designed, among them the trisubstituted-triazole approach, which was found to be the most suitable route. The crucial steps of this approach, the copper-catalyzed azide-haloalkyne cycloaddition and the intramolecular homocoupling reactions, were first studied on a model system; subsequently, this methodology was applied in the synthesis of the desired Nc 2. The increased core size and the π-electron deficient structure predict this class of Ncs to possess very strong aggregation properties. Moreover, owing to the presence of four tridentate half-cavities, the final properties of the molecule or the assembly can, in principle, be further tuned by doping with metals or guest molecules.

  与 1 相比，2 的芳香度增加了四个苯环和八个三唑环，此外，三唑单元和酞菁核共同创造了四个功能性平面空腔。研究人员研究了各种方法，将 1 中相邻三唑的未取代碳原子连接起来，从而得到含有八个融合三唑分子的原子平坦的萘酞菁（Nc）类似物（2）。研究人员设计了几种合成路线，其中三取代三唑法被认为是最合适的路线。首先在一个模型体系上研究了这种方法的关键步骤，即铜催化的叠氮-卤代烃环加成反应和分子内均偶联反应；随后，将这种方法应用于合成所需的 Nc 2。增大的核心尺寸和π-电子缺陷结构预示着这类 Ncs 具有非常强的聚集特性。此外，由于存在四个三叉半腔，原则上可以通过掺杂金属或客体分子来进一步调整分子或组装体的最终特性。
• Synthesis of Dicarboxylate “C-Clamp” 1,2-Diethynylarene Compounds as Potential Transition-Metal Ion Hosts
  作者：Erwin Reisner、Stephen J. Lippard

  DOI：10.1002/ejoc.200700816

  日期：2008.1

  We report an efficient convergent synthesis of a new type of C-clamp ligand with a 1,2-diethynylarene scaffold involving a chelate host capable of binding a guest molecule in its endo-dicarboxylate pocket. The chemistry involves a combination of palladium-catalyzed Sonogashira, Heck, and Suzuki cross-coupling reactions. The compounds 2,3-bis[2-(2′-carboxybiphenyl-4-yl)ethynyl]triptycene and 4,5-bi

  我们报告了一种新型 C 钳配体与 1,2-二乙炔基芳烃支架的高效收敛合成，该支架涉及螯合宿主，能够在其内二羧酸盐口袋中结合客体分子。该化学反应涉及钯催化的 Sonogashira、Heck 和 Suzuki 交叉偶联反应的组合。化合物2,3-双[2-(2'-羧基联苯-4-基)乙炔基]三苯并4,5-双[2-(2'-羧基联苯-4-基)乙炔基]藜芦醇及其2'-羧基-间-三联苯-4-基类似物被设计为双核配体，以组装具有风车几何形状的羧酸根桥接过渡金属配合物。一种含有共结晶水分子的 C 型钳化合物的 X 射线晶体结构揭示了水客体与 C 型钳主体的内取向羧酸实体之间的强氢键。此外，制备了两个syn-N-供体配体作为合成支架，以模拟羧酸桥双核蛋白中N-供体原子的几何排列。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Strain‐Promoted Double Azide Addition to Octadehydrodibenzo[12]annulene Derivatives
  作者：Satomi Fukushima、Minoru Ashizawa、Susumu Kawauchi、Tsuyoshi Michinobu

  DOI：10.1002/hlca.201900016

  日期：2019.4

  Octadehydrodibenzo[12]annulenes (DBAs), readily available by the oxidative acetylenic coupling of 1,2‐diethynylbenzene derivatives, were reacted with organic azides. As compared to the well‐known strain‐promoted azide‐alkyne cycloaddition (SpAAC) of 5,6,11,12‐tetradehydrodibenzo[a,e][8]annulene, the reactivity of the DBA alkynes was lower due to the lower strain energy. However, the regioselective

  1,2-二乙炔基苯衍生物的氧化炔键可轻易获得的十八氢二苯并[12]环戊烯（DBA）与有机叠氮化物反应。与众所周知的应变促进的叠氮化物-炔烃环加成（SpAAC）5,6,11,12-四氢二苯并[ a，e ] [8]环戊烯相比，由于应变较低，DBA炔烃的反应性较低能源。但是，在温和条件下，区域选择性双叠氮化物的添加没有任何副反应，产生了双三唑产物。通过X射线晶体结构分析确认了产物的结构，并通过1研究了反应机理。H-NMR光谱和计算研究。还发现DBA几乎不发荧光，而双三唑产品显示绿色荧光，量子产率高达5.1％。最后，将新的应变促进型双叠氮化物添加到DBA中用于逐步生长聚合，成功生产了高分子量三唑聚合物。
• The Power of Nonconventional Phenyl C–H···N Hydrogen Bonds: Supportive Crystal-Packing Force and Dominant Supramolecular Engineering Force
  作者：Eric Bosch、Nathan P. Bowling、Jeffery Darko

  DOI：10.1021/cg5014076

  日期：2015.4.1

  The role of phenyl C-(HN)-N-... interactions in crystal engineering is explored with a variety of fluorinated phenyl-containing compounds. In particular, we show that this interaction can guide the formation of one-dimensional phenyl C-H...N hydrogen-bonded ribbons with, for example, 4-(2,3,5,6-tetrafluorophenylethynyl)pyridine. The interaction is shown to also control the formation of self-complementary homodimers with 3-(2,3,4,5-tetrafluorophenylethynyl)pyridine. We also demonstrate that the phenyl C-(HN)-N-... hydrogen bond interaction is capable of enticing co-crystallization of molecules such as 2,3,5,6,2',3',5',6'-octafluorobiphenyl and 4,4'-dipyridyl. Finally, we describe the use of an intramolecular scaffold to evaluate the effect of electron-withdrawing substituents on the strength of a phenyl C-(HN)-N-... hydrogen bond.