(1Z,3Z)-1,4-bis(trimethylsilyl)-1,4-diiodo-2,3-dimethyl-1,3-butadiene | 137594-87-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1Z,3Z)-1,4-bis(trimethylsilyl)-1,4-diiodo-2,3-dimethyl-1,3-butadiene
• 英文别名: (1Z,3Z)-1,4-bis(trimethylsilyl)-2,3-dimethyl-1,4-diiodobuta-1,3-diene；[(1Z,3Z)-1,4-diiodo-2,3-dimethyl-4-trimethylsilylbuta-1,3-dienyl]-trimethylsilane
• CAS: 137594-87-7
• 化学式: C₁₂H₂₄I₂Si₂
• 分子量: 478.303
• InChiKey: SBUWXECKMFYENX-WGDLNXRISA-N

物化性质

• 沸点：
  284.5±40.0 °C(Predicted)
• 密度：
  1.484±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.16
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (1Z,3Z)-1,4-bis(trimethylsilyl)-1,4-diiodo-2,3-dimethyl-1,3-butadiene 在 正丁基锂 、 Py(HF)x 、 水 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 23.75h， 生成
  参考文献：
  名称：

  Modification of the electronic structure of silole by the substituents on the ring silicon

  摘要：

  A series of 3,4-dimethyl-2,5-bis(trimethylsilyl)silo having various substituents on the ring silicon atom have been prepared and their UV absorption spectra have been determined. Their absorption maxima steadily shifted to longer wavelengths as the 1,1-substituents on the ring silicon atom become more electronegative. Ab initio calculations at the HF/6-31G(d) level of theory showed that the nature of the 1,1-substituents strongly affects the HOMO and LUMO energy levels of the silole ring mainly due to inductive effects. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00425-2
• 作为产物：
  描述：

  1-(三甲基硅基)丙炔 在 二氯二茂锆 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以77%的产率得到(1Z,3Z)-1,4-bis(trimethylsilyl)-1,4-diiodo-2,3-dimethyl-1,3-butadiene
  参考文献：
  名称：

  Modification of the electronic structure of silole by the substituents on the ring silicon

  摘要：

  A series of 3,4-dimethyl-2,5-bis(trimethylsilyl)silo having various substituents on the ring silicon atom have been prepared and their UV absorption spectra have been determined. Their absorption maxima steadily shifted to longer wavelengths as the 1,1-substituents on the ring silicon atom become more electronegative. Ab initio calculations at the HF/6-31G(d) level of theory showed that the nature of the 1,1-substituents strongly affects the HOMO and LUMO energy levels of the silole ring mainly due to inductive effects. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00425-2

文献信息

• Facile Synthesis of Multiply Substituted Cyclopentadienes and Conjugated Dienals through Reactions between 1,4-Dilithio-1,3-dienes and Carboxylic Acid Derivatives Including Acyl Chlorides, Anhydrides, and DMF
  作者：Chao Wang、Guo-Liang Mao、Zhi-Hui Wang、Zhen-Feng Xi

  DOI：10.1002/ejoc.200600504

  日期：2007.3

  Multiply substituted cyclopentadienes were formed through reactions between phenyl-substituted 1,4-dilithio-1,3-dienes such as 1b and 1c and two molecules of acyl chlorides. The phenyl substituents on the skeletons of the dilithiobutadiene derivatives played an essential role in the reaction pattern. Interestingly, when anhydrides were used, normal alkyl-substituted 1,4-dilithio-1,3-dienes such as

  多取代的环戊二烯是通过苯基取代的 1,4-二硫代-1,3-二烯（如 1b 和 1c）与两分子酰氯之间的反应形成的。二锂硫代丁二烯衍生物骨架上的苯基取代基在反应模式中起重要作用。有趣的是，当使用酸酐时，正常的烷基取代的 1,4-二硫代-1,3-二烯如 1a 也可以与苯基取代的 1b 和 1c 类似地反应，以优异的分离产率提供类似类型的多取代环戊二烯。发现当用 1a-c 处理时，酯可以提供产品的混合物。当 1,4-二锂-1,3-二烯用 DMF 处理时，以良好的收率获得了多取代的 2,4-二烯-1,6-二烯和/或 2,5-二氢呋喃衍生物，
• Synthesis of acenes via coupling of 1,4-dilithiobutadienes with diiodoarenes in the presence of CuCl
  作者：Lishan Zhou、Kiyohiko Nakajima、Ken-ichiro Kanno、Tamotsu Takahashi

  DOI：10.1016/j.tetlet.2009.02.191

  日期：2009.6

  prepared from diiodobutadienes reacted with diiodobenzene or diiodonaphthalene to afford substituted naphthalene, anthracene, dihydronaphthacene, and dihydropentacene derivatives in the presence of CuCl and DMPU. Dihydronaphthacene and dihydropentacene derivatives were converted into the corresponding naphthacene and pentacene derivatives.

  由二碘丁二烯制得的二硫代丁二烯与二碘苯或二碘萘反应，在CuCl和DMPU存在下，得到取代的萘，蒽，二氢萘和二氢并五苯衍生物。将二氢并四苯并二氢并五苯衍生物转化为相应的并四苯并五并苯衍生物。
• 1,3-Butadienylzinc Trimer Formed via Transmetalation from 1,4-Dilithio-1,3-butadienes: Synthesis, Structural Characterization, and Application in Negishi Cross-Coupling
  作者：Yi Zhou、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1021/om3005004

  日期：2012.8.13

  The first well-defined 1,3-butadienylzinc trimers have been synthesized by transmetalation of 1,4-dilithio-1,3-butadienes with 1 equiv of ZnBr2. Their structures have been determined by single-crystal X-ray structural analysis. Their reaction chemistry has been demonstrated by Pd-catalyzed Negishi cross-coupling with iodobenzenes.

  第一个定义明确的1,3-丁二烯基锌三聚体是通过将1，4-二硫代1，3-丁二烯与1当量的ZnBr 2进行金属转移而合成的。它们的结构已经通过单晶X射线结构分析确定。Pd催化的Negishi与碘代苯的交叉偶联已证明了它们的反应化学。
• Cu-Catalyzed Tandem C−N Bond Formation for the Synthesis of Pyrroles and Heteroarylpyrroles
  作者：Rubén Martín、Catharine H. Larsen、Ana Cuenca、Stephen L. Buchwald

  DOI：10.1021/ol7014225

  日期：2007.8.1

  A highly efficient Cu-catalyzed tandem C-N bond-forming reaction of 1,4-dihalo-1,3-dienes has been developed. The transformation allows the synthesis of pyrroles and heteroarylpyrroles with a wide variety of functional groups and substitution patterns from readily available precursors.

  已经开发了一种高效的1,4-二卤代-1,3-二烯的Cu催化串联CN键形成反应。该转化允许从容易获得的前体合成具有多种官能团和取代模式的吡咯和杂芳基吡咯。
• Preparation of Partially Substituted 1-Halo- and 1,4-Dihalo-1,3-dienes via Reagent-Controlled Desilylation of Halogenated 1,3-Dienes
  作者：Zhenfeng Xi、Zhiyi Song、Guangzhen Liu、Xiaozhong Liu、Tamotsu Takahashi

  DOI：10.1021/jo060003f

  日期：2006.4.1

  3-butadienes afforded either 1-halo-1-trimethylsilyl-1,3-butadienes or 1-halo-4-trimethylsilyl-1,3-butadienes in excellent yields with excellent selectivity, respectively, when treated with CF3COOH or with NaOMe. These monosilylated 1,3-butadiene products could be further desilylated to generate their corresponding halobutadienes via the above reagent-controlled desilylation reaction. When 1,4-dihalo-1

  取决于所使用的脱甲硅烷基化试剂，1-卤代-1,4-双（三甲基甲硅烷基）-1,3-丁二烯提供1-卤代-1-三甲基甲硅烷基-1,3-丁二烯或1-卤代-4-三甲基甲硅烷基-1当用CF 3 COOH或NaOMe处理时，分别以优异的收率和优异的选择性获得3,3-丁二烯。这些单甲硅烷基化的1，3-丁二烯产物可以通过上述试剂控制的甲硅烷基化反应进一步被甲硅烷基化以产生其相应的卤代丁二烯。当在室温下用MeONa / MeOH处理1,4-二卤代-1,4-双（三甲基甲硅烷基）-1,3-二烯时，两个三甲基甲硅烷基均发生甲硅烷基化反应，得到相应的1,4-二卤代-1,3-二烯的收率极好。常用的去甲硅烷基化试剂CF 3 COOH不适用于这些二卤双丁二烯。