1-Ethynyl-3,5-bis-triisopropylsilanyloxy-benzene | 429686-59-9

• 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: 1-Ethynyl-3,5-bis-triisopropylsilanyloxy-benzene
• 英文别名: [3-Ethynyl-5-tri(propan-2-yl)silyloxyphenoxy]-tri(propan-2-yl)silane
• CAS: 429686-59-9
• 化学式: C₂₆H₄₆O₂Si₂
• 分子量: 446.821
• InChiKey: VLFPOTFZYMLYTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.78
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Ethynyl-3,5-bis-triisopropylsilanyloxy-benzene 在 正丁基锂 、 N-氯代丁二酰亚胺 作用下， 以 四氢呋喃 为溶剂， 以61%的产率得到((5-(chloroethynyl)-1,3-phenylene)bis(oxy))bis(triisopropylsilane)
  参考文献：
  名称：

  A torquoselective extrusion of isoxazoline N-oxides. Application to the synthesis of aryl vinyl and divinyl ketones for Nazarov cyclization

  摘要：

  A mild, convenient reaction sequence for the synthesis of Nazarov cyclization substrates is described, The [3+2] dipolar cycloaddition of a nitrone and an electron-deficient alkyne gives all isolable isoxazoline intermediate, which upon oxidation undergoes stereoselectivc extrusion of nitrosomethane to give aryl vinyl or divinyl ketones. (C) 2008 Elsevier Ltd. All right, reserved.

  DOI：

  10.1016/j.tet.2008.10.003
• 作为产物：
  描述：

  1-(3,5-bis((triisopropylsilyl)oxy)phenyl)ethan-1-one 在 lithium diisopropyl amide 、 氯磷酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 生成 1-Ethynyl-3,5-bis-triisopropylsilanyloxy-benzene
  参考文献：
  名称：

  A torquoselective extrusion of isoxazoline N-oxides. Application to the synthesis of aryl vinyl and divinyl ketones for Nazarov cyclization

  摘要：

  A mild, convenient reaction sequence for the synthesis of Nazarov cyclization substrates is described, The [3+2] dipolar cycloaddition of a nitrone and an electron-deficient alkyne gives all isolable isoxazoline intermediate, which upon oxidation undergoes stereoselectivc extrusion of nitrosomethane to give aryl vinyl or divinyl ketones. (C) 2008 Elsevier Ltd. All right, reserved.

  DOI：

  10.1016/j.tet.2008.10.003

文献信息

• Polarizing the Nazarov Cyclization:  The Impact of Dienone Substitution Pattern on Reactivity and Selectivity
  作者：Wei He、Ildiko R. Herrick、Tulay A. Atesin、Patrick A. Caruana、Colleen A. Kellenberger、Alison J. Frontier

  DOI：10.1021/ja077162g

  日期：2008.1.1

  The impact of dienone substitution on the Nazarov cyclization has been examined in detail. Substrates bearing different substituents at each of four positions on the dienone backbone were systematically probed in order to identify trends leading to higher reactivity and better selectivity. Desymmetrization of the pentadienyl cation and oxyallyl cation intermediates through placement of polarizing groups

  详细研究了二烯酮取代对 Nazarov 环化的影响。为了确定导致更高反应性和更好选择性的趋势，系统地探测了在二烯酮骨架的四个位置的每个位置上带有不同取代基的底物。发现通过在 C-2 和 C-4 位置放置极化基团使戊二烯基阳离子和氧烯丙基阳离子中间体去对称化特别有效。这些修饰允许在催化量的温和路易斯酸存在下发生环化。还发现亚烷基β-酮酯的E和Z异构体的混合物的立体会聚环化通过在反应条件下发生的有效异构化过程发生。
• End-Cap Stabilized Oligoynes: Model Compounds for the Linear sp Carbon Allotrope Carbyne
  作者：Thomas Gibtner、Frank Hampel、Jean-Paul Gisselbrecht、Andreas Hirsch

  DOI：10.1002/1521-3765(20020118)8:2<408::aid-chem408>3.0.co;2-l

  日期：2002.1.18

  Three series of differently 3,5-disubstituted alpha,omega-diphenylpolyynes Ar-(CdropC)(n)-Ar (n=2, 4, 6, 8, 10) were synthesized under optimized Cadiot-Chodkiewicz conditions, isolated and completely characterized. These compounds can be considered as model substances for the hypothetical one-dimensional carbon allotrope carbyne C, The longest sp-carbon chain contains 20 atoms and is therefore the longest, purely organic polyyne studied with NMR techniques. Extinction coefficients over 600000m(-1)cm(-1) represent the highest measured quantitative values for that compound class so far. Comparisons with previous investigations and electrochemical studies allow the assignment of absorption for both wavelength regions structuring the UV/Vis spectra. Based on the trends in the spectroscopic behaviour of those molecules with increasing chain length. electronic as well as the NMR properties of carbyne are predicted, in line with our previously reported results. The observed stability mise the. properties pro synthesis of even longer polyynes.