4,4'-divinyltolan | 3477-57-4

• 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: 4,4'-divinyltolan
• 英文别名: 1,2-bis(4-vinylphenyl)acetylene；1-Ethenyl-4-[2-(4-ethenylphenyl)ethynyl]benzene
• CAS: 3477-57-4
• 化学式: C₁₈H₁₄
• 分子量: 230.309
• InChiKey: CEHCMLKAHUQTDO-UHFFFAOYSA-N

物化性质

• 熔点：
  138-140 °C
• 沸点：
  377.8±31.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1,1'-(1,2-乙炔二基)二(4-甲基苯) 在 sodium ethanolate 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 4,4'-divinyltolan
  参考文献：
  名称：

  Drefahl,G.; Winnefeld,K., Journal fur praktische Chemie (Leipzig 1954), 1965, vol. 28, p. 242 - 251

  摘要：

  DOI：

文献信息

• Palladium-Catalyzed Efficient and One-Pot Synthesis of Diarylacetylenes from the Reaction of Aryl Chlorides with 2-Methyl-3-butyn-2-ol
  作者：Chenyi Yi、Ruimao Hua、Hanxiang Zeng、Qiufeng Huang

  DOI：10.1002/adsc.200600498

  日期：2007.7.2

  An efficient and practical synthetic method has been developed for the preparation of symmetrical diarylacetylenes from the direct reaction of aryl chlorides with 2-methyl-3-butyn-2-ol catalyzed by palladium(II) chloride-bis(tricyclohexylphosphine) [PdCl2(PCy3)2] under mild reaction conditions. Unsymmetrical diarylated acetylenes could be also obtained by using two different aryl chlorides simultaneously

  已开发出一种有效且实用的合成方法，用于通过氯化钯（II）-双（三环己基膦）[PdCl 2（ PCy 3）2 ]在温和的反应条件下。不对称的二芳基乙炔也可以通过同时使用两种不同的芳基氯化物来获得。催化程序包括一种新型的一锅钯催化的，灭活的芳基氯化物的双Sonogashira双偶联反应，无需使用铜（I）作为助催化剂。
• Syntheses and properties of dumbbell-shaped POSS derivatives linked by luminescent π-conjugated units
  作者：Hitoshi Araki、Kensuke Naka

  DOI：10.1002/pola.26241

  日期：2012.10.15

  isobutyl‐substituted 1,2‐bis(4‐vinylphenyl)acetylene‐linked POSS (DA1), 9,10‐bis(4‐vinylphenyl)ethynyl)anthracene‐linked POSS (DA2), and 5,5″‐bis((4‐vinyl)phenyl)ethynyl)‐2,2′:5′2″‐terthiophene‐linked POSS (DA3), and corresponding model compounds were synthesized by cross metathesis and Sonogashira reaction, and their film formability, and thermal and optical properties were examined. The dumbbell structures of

  哑铃形异丁基取代的1,2-双（4-乙烯基苯基）乙炔连接的POSS（DA1），9,10-双（4-乙烯基苯基）乙炔基）蒽连接的POSS（DA2）和5,5”-通过交叉复分解和Sonogashira反应合成了双（（4-乙烯基）苯基）乙炔基）-2,2'：5'2''-三噻吩连接的POSS（DA3）和相应的模型化合物，并确定了它们的成膜性和热稳定性并检查了光学性质。所得化合物的哑铃结构通过1 H‐，13 C‐和29确认Si-NMR和MALDI-TOF-MS分析 哑铃形的POSS化合物可提供光学透明的薄膜。但是，所有模型化合物均形成不透明的薄膜。所有膜在紫外线辐射下都是发光的。与模型化合物相比，哑铃结构最大程度地减少了较长的波长偏移，并提高了固态发光π共轭连接单元的发射效率。©2012 Wiley Periodicals，Inc. J Polym Sci A部分：Polym Chem，2012年。
• Zinc Chloride‐Promoted Coupling Reaction between Calcium Carbide and Aryl Chlorides
  作者：Tianna Jing、Ning Liu、Caixia Xu、Qingqing Bu

  DOI：10.1002/ejoc.202200178

  日期：2022.6.20

  The palladium-catalyzed coupling reaction of less reactive aryl chlorides by employing calcium carbide as an alkyne source was reported. Various of diarylethynes were obtained in approving yield by addition of ZnCl2, including the desired 1,2-bis(9-anthryl)acetylene, even when being highly sterically hindered

  报道了使用电石作为炔烃源的钯催化的反应性较低的芳基氯化物的偶联反应。通过添加 ZnCl 2获得了各种二芳基乙炔，包括所需的 1,2-双(9-蒽基)乙炔，即使在受到高度空间位阻的情况下也是如此
• Synthetic, Mechanistic, and Computational Investigations of Nitrile-Alkyne Cross-Metathesis
  作者：Andrea M. Geyer、Eric S. Wiedner、J. Brannon Gary、Robyn L. Gdula、Nicola C. Kuhlmann、Marc J. A. Johnson、Barry D. Dunietz、Jeff W. Kampf

  DOI：10.1021/ja800020w

  日期：2008.7.1

  The terminal nitride complexes NW(OC(CF3)(2)Me)(3)(DME) (1-DME), [Li(DME)(2)][NW(OC(CF3)(2)Me)(4)] (2), and [NW(OCMe2CF3)(3)](3) (3) were prepared in good yield by salt elimination from [NWCl3](4). X-ray structures revealed that 1-DME and 2 are monomeric in the solid state. All three complexes catalyze the cross-metathesis of 3-hexyne with assorted nitriles to form propionitrile and the corresponding alkyne. Propylidyne and substituted benzylidyne complexes RCW(OC(CF3)(2)Me)(3) were isolated in good yield upon reaction of 1-DME with 3-hexyne or 1-aryl-1-butyne. The corresponding reactions failed for 3. Instead, EtCW(OC(CF3)Me-2)(3) (6) was prepared via the reaction of W-2(OC(CF3)Me-2)(6) with 3-hexyne at 95 degrees C. Benzylidyne complexes of the form ArCW(OC(CF3)Me-2)(3) (Ar = aryl) then were prepared by treatment of 6 with the appropriate symmetrical alkyne ArCCAr. Three coupled cycles for the interconversion of 1-DME with the corresponding propylidyne and benzylidyne complexes via [2 + 2] cycloaddition-cycloreversion were examined for reversibility. Stoichiometric reactions revealed that both nitrile-alkyne cross-metathesis (NACM) cycles as well as the alkyne cross-metathesis (ACM) cycle operated reversibly in this system. With catalyst 3, depending on the aryl group used, at least one step in one of the NACM cycles was irreversible. In general, catalyst 1-DME afforded more rapid reaction than did 3 under comparable conditions. However, 3 displayed a slightly improved tolerance of polar functional groups than did 1-DME. For both 11-DME and 3, ACM is more rapid than NACM under typical conditions. Alkyne polymerization (AP) is a competing reaction with both 1-DME and 3. It can be suppressed but not entirely eliminated via manipulation of the catalyst concentration. As AP selectively removes 3-hexyne from the system, tandem NACM-ACM-AP can be used to prepare symmetrically substituted alkynes with good selectivity, including an arylene-ethynylene macrocycle. Alternatively, unsymmetrical alkynes of the form EtCCR (R variable) can be prepared with good selectivity via the reaction of RCN with excess 3-hexyne under conditions that suppress AP. DFT calculations support a [2 + 2) cycloaddition-cycloreversion mechanism analogous to that of alkyne metathesis. The barrier to azametalacyciobutadiene ring formation/breakup is greater than that for the corresponding metalacyclobutadiene. Two distinct high-energy azametalacyclobutadiene intermediates were found. These adopted a distorted square pyramidal geometry with significant bond localization.
• Catalytic Nitrile-Alkyne Cross-Metathesis
  作者：Andrea M. Geyer、Robyn L. Gdula、Eric S. Wiedner、Marc J. A. Johnson

  DOI：10.1021/ja0693439

  日期：2007.4.1

  The first catalytic cross-metathesis reaction of an alkyne with a nitrile is described. The nitride complex NW(OC(CF3)(2)CH3)(3)(DME) undergoes reversible triple-bond metathesis reactions with alkynes (RCCR; R = Et, 4-C6H4OMe), forming the alkylidyne complexes RCW(OC(CF3)(2)CH3)(3)(DME) (R = Et, 4-C6H4OMe) along with the corresponding nitrile RCN. This has been exploited to effect catalytic cross-metathesis of nitriles with alkynes, in which the organic CR fragments of two nitriles are coupled to yield an alkyne. A simple "sacrificial" alkyne (3-hexyne) acts as the N-atom acceptor, forming two equivalents of nitrile byproduct (propionitrile).