1-[(1-methyl-1-hydroxyethyl)ethynyl]-2-ethynylbenzene | 288404-66-0

• 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-[(1-methyl-1-hydroxyethyl)ethynyl]-2-ethynylbenzene
• 英文别名: 4-(2-ethynylphenyl)-2-methylbut-3-yn-2-ol
• CAS: 288404-66-0
• 化学式: C₁₃H₁₂O
• 分子量: 184.238
• InChiKey: WXCNNZXOOSAPGC-UHFFFAOYSA-N

物化性质

• 沸点：
  306.3±27.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-[(1-methyl-1-hydroxyethyl)ethynyl]-2-ethynylbenzene 在 bis-triphenylphosphine-palladium(II) chloride 氢氧化钾 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 175.0h， 生成 6,6'-bis[(2-ethynylphenyl)ethynyl]-2,2'-bipyridine
  参考文献：
  名称：

  Twistophane大环具有集成的6,6'-连接的2,2'-联吡啶单元：一种用于金属离子的新型荧光传感器。

  摘要：

  已经合成了新的扭索烷大环2和3；这些化合物由环状共轭脱氢苯并环戊烯骨架组成，该骨架结合了6,6'-连接的2,2'-联吡啶部分，用于配位金属离子。Cyclphanes通过光谱技术表征，并通过分子力学计算显示为螺旋形扭曲，并且手性分子可能以几种可能的基态构象存在。紫外/可见光谱研究表明，2、3和前体9以不同的选择性结合到以下一小组金属分析物的特定成员上：CuII，AgI，HgII，Tl1和PdII。显着地，2、3和9通过荧光发射淬灭输出响应来表示CuII离子的存在。此外，环烷3表现出特别敏感的质子激发的生色荧光响应。关于其独特的结构特征，较高的分析物选择性以及增强的和特征性的荧光发射响应，这些分子是代表化学传感器材料的新铅类的首批实例之一。因此，可以预期化合物2、3和9及其衍生物在金属基环境污染物，生物学上重要的痕量元素和质子通量的检测中将发现许多未来的应用。这些分子是代表化学感应材料的新铅类

  DOI：

  10.1002/1521-3765(20021115)8:22<5250::aid-chem5250>3.0.co;2-q
• 作为产物：
  描述：

  2-methyl-4-(2-((triisopropylsilyl)ethynyl)phenyl)but-3-yn-2-ol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以99%的产率得到1-[(1-methyl-1-hydroxyethyl)ethynyl]-2-ethynylbenzene
  参考文献：
  名称：

  Deltoid versus Rhomboid: Controlling the Shape of Bis-ferrocene Macrocycles by the Bulkiness of the Substituents

  摘要：

  Precise structural control of heteroannularly disubstituted ferrocene (Fc) structures is very challenging as the high rotational mobility of the Fc unit allows a large conformational diversity. Herein we present the syntheses, characterization, and electrochemical investigation of two complementary bis-ferrocene macrocycles, built up via Sonogashira cross coupling and intramolecular ring-closing reaction. While the X-ray structure of 1,2-ethynylbenzene bridged bis-ferrocene complex 1 shows a deltoidal conformation, a stretched oriented rhomboidal bis-ferrocene metalla-cycle 2 is formed when the peripheral benzene rings are decorated with bulky tert-butylsulfanyl groups. VT-NMR spectroscopy is used to assign the rotation of the embedded Fc units in rhomboid 2. Moreover, cyclic voltammetry (CV) of deltoid 1 and rhomboid 2 indicate that electronic communication between both ferrocenyl groups can be neglected, while the electrostatic through space coupling is significant.

  DOI：

  10.1021/acs.organomet.6b00909

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。
• Synthesis of [1,2,3]Triazolo[5,1-<b><i>a</i></b>]isoquinoline Derivatives via a Selective Cascade Cyclization Sequence of 1,2-bis(Phenylethynyl)benzene Derivatives
  作者：Shipeng Tao、Qinquan Hu、Huan Li、Shan Ma、Yunfeng Chen

  DOI：10.1080/00397911.2015.1020952

  日期：2015.6.3

  derivatives, using a selective cascade cyclization of unsymmetrical substituted 1,2-bis(phenylethynyl)benzene derivatives with NaN3, has been developed. The reaction gave different substituted [1,2,3]triazolo[5,1-a]isoquinolines in moderate to good yields. It was found that the substituents on the alkynes were important for the selectivities of the cascade cyclization sequences. GRAPHICAL ABSTRACT

  摘要 采用不对称取代的 1,2-双（苯乙炔基）苯衍生物与 NaN3 的选择性级联环化，一种直接、简洁的合成方法，用于生成 [1,2,3] 三唑并 [5,1-a] 异喹啉衍生物， 已经被开发出来。该反应以中等至良好的产率得到不同的取代的[1,2,3]三唑并[5,1-a]异喹啉。发现炔烃上的取代基对级联环化序列的选择性很重要。图形概要
• Dual Gold-Catalyzed Three-Component Reaction: Efficient Synthesis of Indene-Fused Esters, Acids, and Lactones through Gold Vinylidene Intermediates
  作者：Congjun Yu、Xiaodong Ma、Bin Chen、Bencan Tang、Robert S. Paton、Guozhu Zhang

  DOI：10.1002/ejoc.201700084

  日期：2017.3.17

  A dual gold(I)‐catalyzed three‐component reaction is developed to prepare indene‐fused carboxylic acid derivatives from diynes, alcohols, and pyridine N‐oxides in both inter‐ and intramolecular fashions. Pyridine N‐oxides exhibit unique reactivity and selectivity to oxidize the gold vinylidene. Experimental studies and DFT calculations support ketene formation as the key step.

  开发了一种双金（I）催化的三组分反应，以分子间和分子内方式由二炔，醇和吡啶N-氧化物制备茚稠合的羧酸衍生物。吡啶N-氧化物具有独特的反应性和选择性，可以氧化亚乙烯基金。实验研究和DFT计算支持乙烯酮的形成为关键步骤。
• Syntheses of Acetylenic Oligophenylene Macrocycles Based on a Novel Dewar Benzene Building Block Approach
  作者：Masakazu Ohkita、Kohta Ando、Takanori Suzuki、Takashi Tsuji

  DOI：10.1021/jo0002590

  日期：2000.7.1

  A general synthetic approach to strained p-phenylene-based acetylenic macrocycles is described. A key feature in this approach is exploitation of Dewar benzene as an angular p-phenylene synthon. Thus, 1,4-acetal-bridged 2,5-dichloro(Dewar benzene) 5, prepared in four steps from dimethyl acetylenedicarboxylate and 1,2-dichloroethylene, is applied as such a building block in the syntheses of strained macrocycles 13 and anti-20. For the synthesis of 13, m-phenylene units are used as spacers and modified Eglington-Glaser coupling is applied for the macrocyclization step. For the synthesis of anti-20, on the other hand, o-phenylene units are used as spacers and Sonogashira coupling is applied for the macrocyclization step. Macrocycles 13 and anti-20 are characterized crystallographically? and their strained nature is reflected mainly in the deviation of the acetylene units from linearity; the C=C-C angles range from 168.7(3)degrees to 179.9(3)degrees in 13 and from 168.0(5)degrees to 171.4(4)degrees in anti-20, Macrocycle 13 shows unique conformational property, namely, the p-phenylene units arranged in parallel in the rectangular framework rotate freely about the long axes, as evidenced by the H-1 NMR studies. Macrocycle anti-20 exhibits a Stokes shift of 179 nm, which is exceptionally large for phenylacetylene macrocycles, presumably owing to the characteristic stacking structure.
• Deltoid versus Rhomboid: Controlling the Shape of Bis-ferrocene Macrocycles by the Bulkiness of the Substituents
  作者：Viktor Hoffmann、Loïc le Pleux、Daniel Häussinger、Oliver T. Unke、Alessandro Prescimone、Marcel Mayor

  DOI：10.1021/acs.organomet.6b00909

  日期：2017.2.27

  Precise structural control of heteroannularly disubstituted ferrocene (Fc) structures is very challenging as the high rotational mobility of the Fc unit allows a large conformational diversity. Herein we present the syntheses, characterization, and electrochemical investigation of two complementary bis-ferrocene macrocycles, built up via Sonogashira cross coupling and intramolecular ring-closing reaction. While the X-ray structure of 1,2-ethynylbenzene bridged bis-ferrocene complex 1 shows a deltoidal conformation, a stretched oriented rhomboidal bis-ferrocene metalla-cycle 2 is formed when the peripheral benzene rings are decorated with bulky tert-butylsulfanyl groups. VT-NMR spectroscopy is used to assign the rotation of the embedded Fc units in rhomboid 2. Moreover, cyclic voltammetry (CV) of deltoid 1 and rhomboid 2 indicate that electronic communication between both ferrocenyl groups can be neglected, while the electrostatic through space coupling is significant.