1,8-bis(trimethylsilyl)-3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne | 801287-67-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 1,8-bis(trimethylsilyl)-3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne
• CAS: 801287-67-2
• 化学式: C₂₈H₃₄O₂Si₂
• 分子量: 458.748
• InChiKey: PBQUPKBECCXBQQ-UHFFFAOYSA-N

物化性质

• 沸点：
  505.2±50.0 °C(Predicted)
• 密度：
  1.019±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.84
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,8-bis(trimethylsilyl)-3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne 在 甲醇 、 potassium carbonate 作用下， 以100%的产率得到3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne
  参考文献：
  名称：

  1,4-二炔基丁烯：碳-苯的化学合成，稳定性和前景

  摘要：

  1,4-二炔基丁烯的π电子富集的C 8共轭序列被确定为碳苯衍生物和Diederich的1,4-双（芳基乙炔基）或1,4-双中存在的脆弱而令人着迷的基序（三异丙基甲硅烷基乙炔基）丁三烯被“封端”，特别是在四炔基丁三烯中。对称1,4- dialkynylbutatrienes的家族（E  CC）RCCCCR（CC  E）延伸到功能帽（E = H，CH 3，CCPh，CPhCHBr或CPhCBr 2）与在SP非炔基取代基2个的顶点（R =苯基或CF 3）。选择这些靶标的原因是它们具有吸引人的向碳合成逆向合成路线的潜力-苯，其中芳香族C 18大环将通过顺序复分解或还原偶联过程直接生成。通过用于制备普通丁烯的经典方法（R'Li / CuX介导的宝石-二卤代炔的还原偶联或SnCl 2 / HCl介导的3,6-二氧-辛基还原反应）合成功能性1,4-二炔基丁烯。 -1、4、7-三炔前体

  DOI：

  10.1002/chem.201002769
• 作为产物：
  描述：

  二(三甲基甲硅烷基)乙炔 在 aluminum (III) chloride 、 正丁基锂 、 乙基溴化镁 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 1,8-bis(trimethylsilyl)-3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne
  参考文献：
  名称：

  六芳基-碳-苯的再研究：一种新颖的合成路线，晶体学数据和电化学行为的前景†

  摘要：

  一种改进的12步合成路线和hexaphenyl-的全面表征碳氮化-苯（4，8％）和p -双-3,5-二-叔丁基苯基同源物（11，4％），中描述。该碳氮化-苯参考4现在精确地处于晶体状态通过X射线衍射分析中的手性，空间群描述P 2 1 2 1 2 1，和相比于较少对称衍生物11表现出中心对称填料。根据循环伏安法，六芳基-碳-苯4和11既可以作为可逆的强电子受体，也可以作为标准的电子给体，各自的电位分别为-0.73±1 V和+1.17±2 V / SCE。由于其极低的溶解度，使用“湿法”制造的11层固态膜具有研究电荷传输特性的最初观点，被发现具有较高的粗糙度。

  DOI：

  10.1039/c7nj00028f

文献信息

• Functional [6]Pericyclynes: Synthesis through [14+4] and [8+10] Cyclization Strategies
  作者：Catherine Saccavini、Christine Tedeschi、Luc Maurette、Christine Sui-Seng、Chunhai Zou、Michèle Soleilhavoup、Laure Vendier、Remi Chauvin

  DOI：10.1002/chem.200601191

  日期：2007.6.4

  used [11+7] strategy, the [14+4] and [8+10] strategies were thus explored. They proved to be efficient, affording seven novel hexaoxy[6]pericyclynes corresponding to six different substitution patterns. These compounds were obtained in 7-15 steps as mixtures of stereoisomers. Thus, by using dibenzoylacetylene as the C(4) electrophile, a [14+4] strategy allowed the synthesis of two hexaphenyl representatives

  对合成新型碳苯衍生物的可能策略的关键分析表明，制备[[18] -n] + n]途径有几种制备六氧基[6]-环炔前体的方法。除了先前尝试的[9 + 9]对称方案（n = 9）外，最先选择的策略是n = 1、4、7、10、13和16的那些。含有（19-n）/ 3个三键的C（18-n）ω-双末端的低聚炔，具有含有（n-1）/ 3个三键的C（n）ω-二羰基的ω-双的低聚炔。为了补充先前使用的[11 + 7]策略，因此探索了[14 + 4]和[8 + 10]策略。他们被证明是有效的，提供了对应于六个不同取代模式的七个新颖的六氧[6]环芳烃。这些化合物以7-15个步骤的形式以立体异构体的混合物形式获得。因此，通过使用二苯甲酰基乙炔作为C（4）亲电试剂，[14 + 4]策略允许合成具有两个或四个游离甲醇顶点的两个六苯基代表。该方法还提供了四苯基代表，其中两个剩余的甲氧基顶点被两个炔基或一个4-茴香基和一
• Synthesis and stereochemical resolution of functional [5]pericyclynes
  作者：Luc Maurette、Christine Tedeschi、Emmanuelle Sermot、Michèle Soleilhavoup、Fatima Hussain、Bruno Donnadieu、Remi Chauvin

  DOI：10.1016/j.tet.2004.07.052

  日期：2004.10

  Three different kinds of ring carbo-mers of [5]cyclitol ethers were targeted as challenging examples of functional [5]pericyclynes. Three tertiary pentaaryl-carbo-[5]cyclitol methyl ethers were synthesized through a [11 + 4] ring-closing double addition of triphenyl- and tri-p-anisyl-undecatetrayn-diides to dibenzoyl acetylene. These compounds, obtained as oily mixtures of stereoisomers, are stable and can behave as acetylenic ligands of one or two Co-2(CO)(6) units. NMR analysis reveals that the broad diasteroisomeric dispersity of a triether, is consistently reduced in the symmetrized pentaether. Three bis-secondary triaryl-carbo-[5]cyclitol methyl ethers with adjacent CH(OR) vertices were synthesized through a similar [11 + 4] ring-closing process, where the same tetrayn-diides add to both the carbaldehyde ends of the (eta(2)-OCH-C=C-CHO)Co-2(CO)(6) complex. Despite the possibility of tautomeric isomerization, the occurrence of two adjacent bis-propargylic carbinol vertices does not diminish the stability of the [5]pericyclyne framework. Finally, two bis-secondary carbo-[5]cyclitol methyl ethers with non-adjacent CH(OH) vertices were synthesized through an alternative [10 + 5] ring-closing process. The bis-secondary carbo-[5]cyclitols are regarded as isohypsic equivalents of the challenging [C,C](5)carbo-cyclopentadienyl cation. A diphenyl-hexaoxy-[5]pericyclyne with two non-adjacent secondary carbinol vertices was also prepared through a [10 + 5] ring-closing strategy: this molecule is an isohypsic equivalent of the previously calculated zwitterionic carbo-cyclopentadien one, which could be observed as a DCI/NH3-MS fragment after treatment with SnCl2/HCl. Analytical HPLC showed that the C-11 triphenyl-undecatetrayne precursor of the [11 + 4] strategy was obtained as a statistical 1:2:1 mixture of the three possible diastereoisomers. Semi-preparative HPLC allowed for the resolution of this mixture. The pure major diastereoisomer was employed to prepare a partly resolved sample of pentamethoxy-pentaphenyl-[5]pericyclyne. Analytical HPLC showed that the latter corresponds to the statistical distribution of the expected three residual diastereoisomers. Semi-preparative HPLC finally afforded samples of diastereoisomerically pure pentamethoxy[5]pericyclyne as crystalline solids. (C) 2004 Elsevier Ltd. All rights reserved.