1,6-bis(triisopropylsilyl)hexa-1,5-diyne-3,4-dione | 199275-03-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,6-bis(triisopropylsilyl)hexa-1,5-diyne-3,4-dione
• 英文别名: bis(triisopropylsilyl)hexadiyne-2,3-dione；1,6-bis(triisopropylsilyl)hexa-1,5-diyn-3,4- dione；1,5-Hexadiyne-3,4-dione, 1,6-bis[tris(1-methylethyl)silyl]-；1,6-bis[tri(propan-2-yl)silyl]hexa-1,5-diyne-3,4-dione
• CAS: 199275-03-1
• 化学式: C₂₄H₄₂O₂Si₂
• 分子量: 418.767
• InChiKey: YAEZUESXYBUYSN-UHFFFAOYSA-N

物化性质

• 沸点：
  442.5±28.0 °C(Predicted)
• 密度：
  0.911±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.57
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,6-bis(triisopropylsilyl)hexa-1,5-diyne-3,4-dione 在 molecular sieve 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 溶剂黄146 为溶剂， 反应 2.5h， 生成 6,7-Diethynyl-1,3-dimethylpteridine-2,4-dione
  参考文献：
  名称：

  Synthesis and Cyclization of Novel Lumazine - Enediyne Chimeras

  摘要：

  DOI：

  10.3987/com-98-8375
• 作为产物：
  描述：

  草酰氯 、 三异丙基硅基乙炔 在 正丁基锂 、 copper(I) bromide 、 lithium bromide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.5h， 以83%的产率得到1,6-bis(triisopropylsilyl)hexa-1,5-diyne-3,4-dione
  参考文献：
  名称：

  通过钼羰基介导的串联 Allenic Pauson-Khand 反应合成双环戊二烯 [a,e] 戊烯和平面双环戊二烯 [a,e] 戊烯的 X 射线晶体结构

  摘要：

  已经合成了属于双环戊二烯 [a,e] 戊烯家族的两个 14 pi 交联环烯，14 pi 双烯醇三氟甲磺酸酯 27 和 3,7-二异丙基甲硅烷基取代的 14 pi 双环戊二烯 [a,e] 戊烯 30。由Mo(CO)(6) 介导的新的allenic 串联Pauson-Khand 反应被用作构建四环的核心的关键过程。正如 27 的 X 射线结构所揭示的那样，两个线性双环戊二烯 [a,e] 戊烯 27 和 30 经历了显着的电子离域，甚至可能是芳香性的。27 中的四环呈现平面几何形状（图 4）；27 中四环的键长也非常符合芳香族化合物的标准。27 和 30 的 NMR 和 UV 光谱的比较表明它们都表现出相似的电子特性，因此，

  DOI：

  10.1021/ja040120x

文献信息

• Acetylene-substituted pyrazino[2,3-f][1,10]phenanthrolines and their Ru(ii) complexes: syntheses, electronic properties and an exploration of their suitability as building blocks for metal-coordinated dehydroannulenes
  作者：Rüdiger Faust、Sascha Ott

  DOI：10.1039/b110660k

  日期：2002.4.26

  Aryl- and silyl-terminated 6,7-dialkynylpyrazino[2,3-f][1,10]phenanthrolines (pyzphen) have been prepared by the condensation of [1,10]phenanthroline-5,6-diamine with appropriately functionalised dialkynyl-1,2-diones. These new ligands were used as chelators in the formation of the corresponding [Ru(bpy)2(pyzphen)]·2PF6 and [Ru(phen)2(pyzphen)]·2PF6 complexes. The terminally free diethynyl [Ru(bpy)2(pyzphen)] complex, obtained by protodesilylation of a silyl-protected precursor, was shown to be amenable to oxidative acetylene hetero-coupling reactions with arylacetylenes and allowed the preparation of the corresponding butadiynyl-substituted derivatives. Homo-coupling reactions of the terminally free diethynyl [Ru(bpy)2(pyzphen)] complex to produce cyclic dehydroannulene-arrays were successful, but furnished an inseparable mixture of compounds of at least two different ring sizes. The photophysical and electrochemical properties of both the free ligands and their Ru(II)-complexes are clearly modified by the presence of the alkynyl substituents. In comparison with non-acetylenic model compounds it was established that acetylene substitution induces bathochromically shifted electronic absorptions and emissions to various degrees in ligands and complexes, leads to increased luminescence lifetimes and quantum yields of the ruthenium pyzphen complexes, and renders the acetylenic ligands and their complexes more susceptible to electrochemical reduction.

  终端为芳基和硅基的6,7-二炔基吡咯啉[2,3-f][1,10]菲啰啉（pyzphen）是通过将[1,10]菲啰啉-5,6-二胺与适当功能化的二炔基-1,2-二酮缩合而制备的。这些新配体作为螯合剂，用于形成相应的[Ru(bpy)2(pyzphen)]·2PF6和[Ru(phen)2(pyzphen)]·2PF6复合物。通过对硅基保护前体进行去硅化反应获得的终端自由的二炔基[Ru(bpy)2(pyzphen)]复合物，显示出能够与芳基炔烃进行氧化乙炔异聚合反应，从而制备了相应的丁炔基取代衍生物。终端自由的二炔基[Ru(bpy)2(pyzphen)]复合物的异聚反应成功地产生了环状脱氢环烷烃阵列，但得到的化合物为至少两种不同环大小的不可分离混合物。自由配体及其Ru(II)复合物的光物理和电化学性质明显受到炔基取代基的影响。与非炔基模型化合物相比，结果表明，炔基取代会在配体和复合物中以不同程度引起电子吸收和发射的红移，增加了锆吡咯啉复合物的发光寿命和量子产率，并使炔基配体及其复合物对电化学还原更为敏感。
• Synthesis of a highly strained permethylenated cycloocta-1,5-diyne derivative by acid-catalysed thermal rearrangement
  作者：Stefan Kammermeier、Peter Siemsen、Paul Seiler、François Diederich、Rik R. Tykwinski

  DOI：10.1039/a802927j

  日期：——

  Preparation of a dimeric derivative of 1,1,2,2-tetraethynylethane (3,4-diethynylhexa-1,5-diyne) and its unexpected rearrangement to a permethylenated cycloocta-1,5-diyne, the structure of which was confirmed by X-ray crystallography, is reported.

  报告了1,1,2,2-四乙炔乙烷（3,4-二乙炔己-1,5-二炔）的二聚体衍生物的制备及其意外重排形成一个全甲基化的环辛-1,5-二炔，其结构通过X射线晶体学得到了证实。
• One-step synthesis of dialkynyl-1,2-diones and their conversion to fused pyrazines bearing enediyne units
  作者：Rüdiger Faust、Christian Weber、Vito Fiandanese、Giuseppe Marchese、Angela Punzi

  DOI：10.1016/s0040-4020(97)01007-7

  日期：1997.10

  and oxalyl chloride in the presence of CuBr and LiBr is described. The condensation of 3 with various aromatic and heteroaromatic 1,2-diamines leads to pyrazine-based α-dialkynylated heterocycles. The enediyne substructure of diethynylquinoxaline can be thermally rearranged in a Bergman cyclization reaction.

  描述了在CuBr和LiBr存在下由乙炔锂和草酰氯制备对称的末端保护的二炔基1,2-二酮3的简便方法。3与各种芳族和杂芳族1,2-二胺的缩合导致形成吡嗪基α-二炔基化杂环。二乙炔基喹喔啉的烯二炔亚结构可以在Bergman环化反应中进行热重排。
• The Synthesis of a Dicyclopenta[<i>a</i>,<i>e</i>]pentalene via a Molybdenum Hexacarbonyl-Mediated Tandem Allenic Pauson−Khand Reaction
  作者：Hui Cao、Judith Flippen-Anderson、James M. Cook

  DOI：10.1021/ja021159+

  日期：2003.3.1

  An approach to the 14pi annulene has been developed, by employing the molybdenum hexacarbonyl-mediated tandem allenic Pauson-Khand reaction as a key step. A di-triisopropylsilyl substituted dicyclopenta[a,e]pentalene was synthesized. This 14pi annulene showed some electronic delocalization, which was not observed in previous cases.

  通过采用六羰基钼介导的串联丙二烯 Pauson-Khand 反应作为关键步骤，开发了一种 14pi 环烯的方法。合成了二-三异丙基甲硅烷基取代的二环戊二烯[a，e]戊烯。这个 14pi 环烯显示出一些电子离域，这在以前的情况下是没有观察到的。
• NIR chromophores from small acetylenic building blocks: a Diels–Alder approach to octaalkynylphthalocyanines
  作者：Rüdiger Faust、Frieder Mitzel

  DOI：10.1039/b006114j

  日期：——

  Two new routes to cross-conjugated 3,4-dimethylenehexa-1,5-diynes, both starting from dialkynyl 1,2-diones, have been devised. Whereas triisopropylsilyl-protected diketones could be diolefinated in a bis-Wittig reaction with methylenetriphenylphosphorane, their aryl-terminated congeners had to be subjected to the conditions of the Peterson olefination (trimethylsilylmethylmagnesium chloride and subsequent dehydration of the resulting diol with thionyl chloride). The reactivity of the diethynylbutadienes towards standard dienophiles was found to be low and alternative thermal reactions compete with [4 + 2] cycloadditions. However, dicyanoacetylene was shown to be an effective cycloaddition partner leading, after aromatisation, to the corresponding dicyanodiethynylbenzenes. These were cyclotetramerised with magnesium butanolate in butanol to furnish octaalkynylphthalocyanines, thereby completing a concise, three-step synthesis of these NIR chromophores of relevance to photodynamic forms of therapy.

  研究人员设计了两条新的路线，从 1,2 二炔基二酮出发，制备交叉共轭的 3,4-二亚甲基六-1,5-二炔。三异丙基硅烷保护的二酮类化合物可以在与亚甲基三苯基膦的双维蒂希反应中进行二烯化反应，而其芳基封端的同系物则必须在彼得森烯化反应的条件下进行（三甲基硅甲基氯化镁，然后用亚硫酰氯对生成的二元醇进行脱水）。研究发现，二炔丁二烯与标准亲二烯的反应活性较低，替代热反应与[4Â +Â 2]环加成反应存在竞争。不过，二氰基乙炔被证明是一种有效的环加成伙伴，经过芳香化后可生成相应的二氰基二炔基苯。这些化合物在丁醇中与丁酸镁发生环四聚反应，生成八烷基炔基酞菁，从而完成了与光动力疗法相关的近红外发色团的简明三步合成。