3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne | 801287-69-4

• 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: 3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne
• 英文别名: (3,6-Dimethoxy-6-phenylocta-1,4,7-triyn-3-yl)benzene；(3,6-dimethoxy-6-phenylocta-1,4,7-triyn-3-yl)benzene
• CAS: 801287-69-4
• 化学式: C₂₂H₁₈O₂
• 分子量: 314.384
• InChiKey: VNYRGMNNVUHPEE-UHFFFAOYSA-N

物化性质

• 沸点：
  441.6±45.0 °C(Predicted)
• 密度：
  1.121±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,6-dimethoxy-3,6-diphenylocta-1,4,7-triyne 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.5h， 生成 12,15-dimethoxy-12,15-diphenyl-3,3-dimethyl-1,5-dioxaspiro[5,14]icosa-7,10,13,16,19-pentayne-9,18-diol
  参考文献：
  名称：

  Synthesis and stereochemical resolution of functional [5]pericyclynes

  摘要：

  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.

  DOI：

  10.1016/j.tet.2004.07.052
• 作为产物：
  描述：

  3-phenyl-1-(trimethylsilyl)penta-1,4-diyn-3-ol 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

文献信息

• 1,4-Dialkynylbutatrienes: Synthesis, Stability, and Perspectives in the Chemistry of carbo-Benzenes
  作者：Valérie Maraval、Léo Leroyer、Aya Harano、Cécile Barthes、Alix Saquet、Carine Duhayon、Teruo Shinmyozu、Remi Chauvin

  DOI：10.1002/chem.201002769

  日期：2011.4.26

  The π‐electron‐rich C8‐conjugated sequence of 1,4‐dialkynylbutatrienes is identified as a fragile and fascinating motif occurring in carbo‐benzene derivatives, and in Diederich’s 1,4‐bis(arylethynyl)‐ or 1,4‐bis(triisopropylsilylethynyl)butatriene “capped” representatives, in particular, in tetraalkynylbutatriene. The family of symmetrical 1,4‐dialkynylbutatrienes (ECC)RCCCCR(CCE) is extended

  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
• <i>Carbo</i>-siloles, Part 2: Synthesis and Stereochemical Resolution of a <i>Carbo</i>-silolane Redox Equivalent
  作者：Catherine Saccavini、Christine Tedeschi、Christine Lepetit、Leila Yahi、Caroline Pistre、Valérie Maraval、Remi Chauvin

  DOI：10.1080/10426500902947922

  日期：2009.6.23

  eliminative aromatization of sila[5]pericyclyne precursors with adjacent C─OR and C─H vertices. The synthesis of tetraoxy-sila[5]pericyclyne representatives (“carbo-silolanes” 2a and 2b ) has been tackled through several [(15–n)+n] ring formation strategies. After having first attempted a [14+1] route from dichlorodiphenylsilane and a skipped pentayne ( 3 ), a [5+10] route proceeded successfully from

  Carbo-siloles 可以通过 sila[5]pericyclyne 前体与相邻的 C─OR 和 C─H 顶点的消除芳构化产生。四氧硅[5]环炔代表（“碳硅酮”2a和2b）的合成已经通过几种[(15-n)+n]成环策略得到解决。在首先尝试从二氯二苯基硅烷和跳过的戊炔 (3) 开始的 [14+1] 路线后，从二乙炔二苯基硅烷 (7) 和三炔二醇 (4) 成功地进行了 [5+10] 路线，得到了硅 [5] 环炔二醇(2a) 作为六种非对映异构体的混合物，产率为 20%。连续色谱提供了一种纯的 2a 非对映异构体。模型二羟基、二甲氧基碳硅烷的 DFT 计算表明碳聚合物五元环的包络构象。2a 的两个仲甲醇顶点的甲基化以 68% 的产率提供了相应的四甲氧基碳硅烷 (2b)。用 Et 2 O·BF 3 的 2b 处理芳构化为目标碳-硅酮被证明是笨拙的。
• 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。
• Expanding the <i>carbo</i> ‐Benzene Chemical Space for Electron‐Accepting Ability: Trifluorotolyl/Tertiobutyl Substitution Balance
  作者：Marwa Chammam、Irving Caballero‐Quintana、Denisse Barreiro‐Argüelles、Olivia Amargós‐Reyes、Youssef Aidibi、Brice Kauffmann、Carine Duhayon、José‐Luis Maldonado、Gabriel Ramos‐Ortíz、Valérie Maraval、Remi Chauvin

  DOI：10.1002/hlca.201900049

  日期：2019.5

  the lipophilicity and electron accepting ability of the tetraphenyl‐carbo‐benzene scaffold, peripheral fluorination of the C18 ring through aromatic linkers was envisaged from the C18Ph6 and o‐tBu2C18Ph4 references, by replacement of two Ph substituents with two p‐CF3‐C6H4 counterparts (FTol). The synthesis relied on a [8+10] macrocyclization involving a common bis(trifluorotolyl)‐tetraynedione, followed

  为了改变四苯基碳苯骨架的亲脂性和电子接受能力，从C 18 Ph 6和o - t Bu 2 C 18 Ph 4参考文献中设想了通过芳族接头对C 18环进行周边氟化，通过用两个p- CF 3 -C 6 H 4对应物替换两个Ph取代基（FTol）。合成依赖于[8 + 10]大环化，包括常见的双（三氟甲苯基）-丁炔二酮，然后还原所得[6]环炔二醇的芳构化。虽然由于极低的溶解度而证明p ‐ F Tol 2 C 18 Ph 4很难处理，但是可以通过X射线晶体学，NMR和UV广泛研究p ‐ F Tol 2 ‐ o - t Bu 2 C 18 Ph 2。 / Vis光谱，伏安法，单层STM成像以及使用P3HT或PC 71的二元膜的AFM成像通过旋涂制造的用于有机光伏电池的BM及其J - V曲线测量。电子和极性特性与CF 3基团的中等但一致的吸电子效应相关，这与DFT计算的边界轨道和多极矩一致。结果为优化氟化碳苯目标提供了指导。