1-trimethylsilyl-3-phenyl-3-methoxypenta-1,4-diyne | 165055-35-6

• 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-trimethylsilyl-3-phenyl-3-methoxypenta-1,4-diyne
• 英文别名: (3-Methoxy-3-phenylpenta-1,4-diyn-1-yl)(trimethyl)silane；(3-methoxy-3-phenylpenta-1,4-diynyl)-trimethylsilane
• CAS: 165055-35-6
• 化学式: C₁₅H₁₈OSi
• 分子量: 242.393
• InChiKey: BSFIRKQLXAJJFG-UHFFFAOYSA-N

物化性质

• 沸点：
  294.2±40.0 °C(Predicted)
• 密度：
  0.978±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.04
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-trimethylsilyl-3-phenyl-3-methoxypenta-1,4-diyne 在 正丁基锂 、 乙基溴化镁 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 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
• 作为产物：
  描述：

  3-(trimethylsilyl)-1-phenyl-2-propyn-1-one 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 15.17h， 生成 1-trimethylsilyl-3-phenyl-3-methoxypenta-1,4-diyne
  参考文献：
  名称：

  的合成，结构和3,9,15三-和属性3,6,9,12,15,18-六取代dodecadehydro [18]轮烯（C 18 H ^ 3 - [R 3和C 18 - [R 6）与d 6H -对称

  摘要：

  3,9,15三（p -叔丁基苯基）dodecadehydro [18]轮烯（6）和3,6,9,12,15,18-六取代的dodecadehydro [18]轮烯（7,8，和9）已经准备好了。已显示这些化合物可加热至150°C，而不会分解。X射线晶体学确定7的分子结构，表明7具有D 6h对称性的平面π系统。UV和NMR光谱数据表明这四种化合物具有高的热稳定性和构象稳定性以及强的反磁性感应环电流。

  DOI：

  10.1016/s0040-4020(98)00011-8

文献信息

• Synthesis of the first 3,6,9,15,18,18-hexa-substituted-1,2,4,5,7,8,10,11,13,14,16,17-dodecadehydro[18]annulenes with D6h-symmetry
  作者：Yoshiyuki Kuwatani、Naoto Watanabe、Ikuo Ueda

  DOI：10.1016/0040-4039(94)02181-a

  日期：1995.1

  3,6,9,12,15,18-Hexaphenyl-1,2,4,5,7,8,10,11,13,14,16,17-dodecadehydro[18]annulene and related compounds have been synthesized. These compounds were found to be stable both in crystalline forms and chloroform solution at room temperature, to have aromatic character by the existance of a diamagnetic ring current on the basis of the nmr spectral data, and to conform to the D6h-symmetry group.

  合成了3,6,9,12,15,18-六苯基-1,2,4,5,7,8,10,11,13,14,16,17-十二烷基氢化[18]环戊烯和相关化合物。发现这些化合物是稳定的无论是在结晶形式，并在室温氯仿溶液，通过NMR谱数据的基础上形成的反磁性环电流是否存在等具有芳香性，和以符合d 6H -symmetry基。
• 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
• Aromatic Rings and Aromatic Rods: Nonplanar Character of an Indeno-dehydro[14]annulene
  作者：Valérie Maraval、Remi Chauvin、Kévin Cocq、Nathalie Saffon-Merceron、Albert Poater

  DOI：10.1055/s-0035-1562720

  日期：——

  Since the concept of aromaticity has been proposed to be generalizable to acetylenic rods (‘linear ring’ of [2]annulene), p-diisopropyl-tetraphenyl-carbo-benzene (C48H34) and an indenone-fused isopropyl-triphenyloctadehydro[14]annulene (C42H26O) can be regarded as based on heptacyclic aromatic cores. The formation and X-ray crystal structures of both products are described. The latter has been obtained

  由于芳香性的概念已被提议推广到炔棒（[2] 环烯的“线性环”）、对二异丙基四苯基碳苯 (C48H34) 和茚酮稠合的异丙基三苯基八氢[14] 环烯(C42H26O) 可以被认为是基于七环芳香核。描述了两种产品的形成和 X 射线晶体结构。后者是作为瞬态异丙基-戊氧基 [5] 环炔烃的还原重排产物获得的，该产物被设计为碳富烯靶标的推定前体。提出了一种解释这种特殊转变的机制。通过茚酮双环的平均平面与 [14] 环大环的 13 个原子的平均平面之间的 6° 角来测量与全局平面度的偏差，与异丙基取代的 sp2 顶点的局部平面分别形成 16° 和 15° 的二面角。碳苯和茚八氢[14] 环烯产品的磁性芳香性通过 NICS 计算进行评估。
• 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.
• Solid-Phase Synthesis of Homogeneous Ruthenium Catalysts on Silica for the Continuous Asymmetric Transfer Hydrogenation Reaction
  作者：Albertus J. Sandee、Daniëlle G. I. Petra、Joost N. H. Reek、Paul C. J. Kamer、Piet W. N. M. van Leeuwen

  DOI：10.1002/1521-3765(20010316)7:6<1202::aid-chem1202>3.3.co;2-i

  日期：2001.3.16

  The solid-phase synthesis of new asymmetric transfer hydrogenation catalysts as well as the use of these silica supported systems in batch and flow reactors is reported. The ruthenium complex of NH-benzyl-(1R,2S)-(-)-norephedrine covalently tethered to silica showed a high activity and enantioselectivity in the reduction of acetophenone. In three consecutive batchwise catalytic runs, we obtained ee values 88%. In a continuous flow reactor, a very constant catalytic activity was observed; no catalyst deactivation occurred over a period of one week, This has been ascribed to successful site isolation. Using optimized conditions in this flow reactor, the ee was as high as 90% at 95% conversion, The supported catalysts generally show the same trend in catalyst performance as in solution. The viability of our approach was further shown in one example, the ruthenium(II) complex of (1S,2R)-(+)-2-amino-1,2-diphenylethanol, for which an enantiomeric excess of 58% was observed, which is nearly three times higher than its homogeneous analogue.