1,2-bis(trimethylsilylethynyl)benzene | 73392-23-1

• 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: 1,2-bis(trimethylsilylethynyl)benzene
• 英文别名: o-bis(trimethylsilylethynyl)benzene；1,2-Bis((trimethylsilyl)ethynyl)benzene；trimethyl-[2-[2-(2-trimethylsilylethynyl)phenyl]ethynyl]silane
• CAS: 73392-23-1
• 化学式: C₁₆H₂₂Si₂
• 分子量: 270.522
• InChiKey: AOXOMZYRICNLQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  1,2-bis(trimethylsilylethynyl)benzene 在 氢氧化钾 、 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲醇 、 邻二氯苯 为溶剂， 反应 0.5h， 生成 [4.4]orthocyclopha-1,3,11,13-tetrayne
  参考文献：
  名称：

  Synthesis of Diacetylene Macrocycles Derived from 1,2-Diethynyl Benzene Derivatives: Structure and Reactivity of the Strained Cyclic Dimer

  摘要：

  Diacetylene macrocycles 2-4 (n = 1-3) (R = H, C4H9, C6H13, C10H21, C12H25, OC10H21) have been prepared from the oxidative coupling of 1,2-diethynylbenzene derivatives. These compounds can be produced in useful quantities and are of interest as precursors to novel conjugated organic polymers. The reported results indicate that when the R groups are large the dimeric macrocycle (n = 1) can be prepared in as high as 74% yield from the corresponding 1,2-diethynylbenzene in a one-step procedure. An alternate multistep procedure was found to produce the tetrameric macrocycle (n = 3, R = C6H13) in 45 % yield. The highly strained dimeric macrocycle was characterized by an X-ray structure and was found to be very reactive. The dimers undergo a rapid very exothermic polymerization at 100-125-degrees-C, indicative of a chain reaction. Reaction of the dimeric macrocycles with iodine results in intramolecular cyclization and a new 20pi electron tetraiodide fused ring system. Reaction of the tetraiodide with oxygen produces a related compound in which two of the iodides have been converted to ketones.

  DOI：

  10.1021/jo00085a016
• 作为产物：
  描述：

  1,2-二溴苯 在 四(三苯基膦)钯 正丙胺 作用下， 反应 22.0h， 生成 1,2-bis(trimethylsilylethynyl)benzene
  参考文献：
  名称：

  The synthesis of 11-13-membered diacetylenic and 18-membered tetraacetylenic ring systems

  摘要：

  DOI：

  10.1016/s0040-4039(00)96842-4

文献信息

• A Versatile Route to 3-Benzoheteroepines Containing Group 15 and 16 Heavier Elements Involving Several Novel Ring Systems, and Their Thermal Stabilities
  作者：Shuji Yasuike、Tsutomu Kiharada、Takashi Tsuchiya、Jyoji Kurita

  DOI：10.1248/cpb.51.1283

  日期：——

  The C-unsubstituted 3-benzoheteroepines (2a-g) containing group 15 (P, As, Sb, and Bi) and group 16 (S, Se, and Te) heavier elements were prepared by the reaction of the corresponding metal reagents with (Z,Z)-o-bis(beta-lithiovinyl)benzene (5) which was derived in two steps from a common o-phthalaldehyde (3). The heteroepines (2) thus obtained were thermally labile towards heteroatom extrusion, and

  通过使相应的金属试剂与（）进行反应，制得含有15组（P，As，Sb和Bi）和16组（S，Se和Te）较重元素的C-未取代的3-苯并杂庚烷（2a-g）。 Z，Z）-邻-双（β-硫代乙烯基）苯（5）分两步衍生自常见的邻苯二甲醛（3）。如此获得的异戊二烯（2）对杂原子挤出具有热稳定性，并且根据（1）H-NMR谱分析估计，它们的加热半衰期表明，3-苯并杂庚烷（2）的稳定性远不及相应的1-苯并杂庚烷（1）。含Sb，Bi和Te的2,4-双（三甲基甲硅烷基）-3-苯并杂庚烷（17）也是由邻二碘苯（9）分6个步骤制备的，发现比相应的C-未取代的杂庚烷更稳定（2）。
• 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。
• CO Extrusion in Homogeneous Gold Catalysis: Reactivity of Gold Acyl Species Generated through Water Addition to Gold Vinylidenes
  作者：Janina Bucher、Tim Stößer、Matthias Rudolph、Frank Rominger、A. Stephen K. Hashmi

  DOI：10.1002/anie.201409859

  日期：2015.1.26

  describe a new gold‐catalyzed decarbonylative indene synthesis. Synergistic σ,π‐activation of diyne substrates leads to gold vinylidene intermediates, which upon addition of water are transformed into gold acyl species, a type of organogold compound hitherto only scarcely reported. The latter are shown to undergo extrusion of CO, an elementary step completely unknown for homogeneous gold catalysis. By tuning

  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。
• Metallorganische verbindungen des 1,2-diethinylbenzols vom typ o-C6H4(CCMR3)2 (M = Si, Ge, Pb)
  作者：R. Nast、H. Grouthi

  DOI：10.1016/s0022-328x(00)89868-x

  日期：1980.2

  The preparation of the compounds o-C6H4(CCMR3)2 (M = Si, Ge, Pb; R = CH3; M = Pb; R = C6H5) is described. Their properties are compared with those of o-C6H4(CCSnR3)2 (R = CH3, C6H5) and those of their p-isomers. The structures and bonding conditions proposed for these molecules are supported by dipole measurements, mass spectroscopy, IR, Raman, 1H NMR and 13C NMR data.

  描述了化合物o -C 6 H 4（C ＝CMR 3）2（M ＝ Si，Ge，Pb； R ＝ CH 3； M ＝ Pb； R ＝ C 6 H 5）的制备。它们的性能与那些相比ö -C 6 ħ 4（CCSnR 3）2（R = CH 3，C 6 H ^ 5）和他们的p -异构体。偶极测量，质谱，IR，拉曼，1 H NMR和13支持了针对这些分子提出的结构和键合条件。1 H NMR数据。
• Synthesis of polyphenylene derivatives by thermolysis of enediynes and dialkynylaromatic monomers
  作者：Jens A John、James M Tour

  DOI：10.1016/s0040-4020(97)00977-0

  日期：1997.11

  Described are the syntheses of substituted enediynes and dialkynylaromatics using Pd- or cross coupling procedures. The products were then thermalized to afford the corresponding poly(p-phenylene)s, poly(1,4-naphthalene)s, poly(benzo[c]thiophene)s, and poly(dibenzothiophene)s. Fifteen examples are provided that show the scope of the polymerization process based upon substituent patterns and cyclization

  描述了使用Pd-或交叉偶联方法的取代烯二炔和二炔炔衍生物的合成。然后将产物加热，得到相应的聚（对苯撑），聚（1,4-萘），聚（苯并[ c]]噻吩和聚（二苯并噻吩）。提供了十五个实例，其基于取代基图案和环化部分显示了聚合过程的范围。使用热重分析法证明了新衍生的聚合物具有极好的热回弹性。通常使用与聚合物重复单元结构相似的小分子的红外数据相关性来确定聚合物的结构。由GCMS分析的二聚中间体的自由基捕获进一步证实了所提出的机理路线。通过监测单体消耗程度相对于聚合物分子量来确定逐步增长的聚合方式。