1,8-di-p-tolylocta-1,3,5,7-tetrayne | 1301149-24-5

• 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: 1,8-di-p-tolylocta-1,3,5,7-tetrayne
• 英文别名: 1,8‐di‐ptolylocta‐1,3,5,7‐tetrayne；1,8-di(p-tolyl)-1,3,5,7-octatetrayne；1-Methyl-4-[8-(4-methylphenyl)octa-1,3,5,7-tetraynyl]benzene；1-methyl-4-[8-(4-methylphenyl)octa-1,3,5,7-tetraynyl]benzene
• CAS: 1301149-24-5
• 化学式: C₂₂H₁₄
• 分子量: 278.353
• InChiKey: VXWUODATXXKKLK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-(buta-1,3-diyn-1-yl)-4-methylbenzene 在 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 丙酮 为溶剂， 反应 4.0h， 以0.108 g的产率得到1,8-di-p-tolylocta-1,3,5,7-tetrayne
  参考文献：
  名称：

  Synthesis, photophysics and excited state structure of 1,8-di(p-tolyl)-1,3,5,7-octatetrayne

  摘要：

  The Cadiot-Chodkiewicz type C-2-elongation of p-tolylacetylene followed by dimerization of the resulted diyne p-CH3C6H4(C =C)(2)TMS (1) gave thermally stable octatetrayne p-CH3C6H4(C C)(4)-p-C6H4H3 (2) as light yellow powder in 75% yield. Compound 2 was characterized by spectroscopic methods and X-ray crystallography. Careful analysis of the crystal data revealed high degree of chain linearity with a potential for 1,n-topochemical polymerization. Next, photophysical properties of 2 were studied in details by experimental and advanced theoretical methods (ab initio HF as well as DFT calculations involving both the ground and excited state geometry optimization). These properties are similar to the properties of the parent polyyne C6H5(C C)(4)C6H5 previously described in literature (in particular, the lowest electronic excited singlet state (S-1) of 2 is a dark state). This was confirmed by the experimental facts, namely, few progressions of the stretching mode (a(g)) of the polyyne chain, starting from different "false origins" lying below the second excited (bright) state (S-2), were observed in the fluorescence excitation spectrum. The red shift of the electronic spectra (155 cm(-1) and 300 cm(-1) for absorption and fluorescence, respectively) and an increase of an energy gap between SI and 52 states by 450 cm(-1) are the effects of methylation of C6H5(C C)(4)C6H5 to 2. Theoretical results showed that in the excited state of 2 a shortening of single bonds and elongation of triple bonds occurred. This is in accordance with an observation of a long progression of the stretching vibration mode in the experimental absorption spectrum of 2. Besides that, stretching vibration of the polyyne chain is also active in the fluorescence spectra. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jphotochem.2010.10.023

文献信息

• Mori-Hiyama versus Hay Coupling for Higher Polyynes
  作者：Nurbey Gulia、Karolina Osowska、Bartłomiej Pigulski、Tadeusz Lis、Zbigniew Galewski、Sławomir Szafert

  DOI：10.1002/ejoc.201200554

  日期：2012.9

  C6H9 (4), p-CH3OC6H4 (5), p-C6H5COC6H4 (6), p-NO2C6H4 (7), and p-NCC6H4 (8)] by Hay coupling with in situ deprotection gave stable octatetraynes R(C≡C)4R (1–8-C8-1–8) in 42–80 % yields as light yellow to brown powders. The same tetraynes were next synthesized from the same C4 precursors by an alternative Mori–Hiyama method that typically utilizes trimethylsilyl-substituted alkynes without prior deprotection

  C4前体RC≡CC≡CTMS的二聚化 [R = C6H5 (1), p-CH3C6H5, (2), 4-n-C5H11C6H4 (3), C6H9 (4), p-CH3OC6H4 (5), p-C6H5COC6H4 ( 6)、p-NO2C6H4 (7) 和 p-NCC6H4 (8)] 通过 Hay 偶联与原位脱保护在 42-80 中得到稳定的辛四炔 R(C≡C)4R (1-8-C8-1-8) % 产量为浅黄色至棕色粉末。接下来通过另一种 Mori-Hiyama 方法从相同的 C4 前体合成相同的四炔，该方法通常使用三甲基甲硅烷基取代的炔烃，无需事先脱保护。后一种方案证明是有用的，并提供了预期的产品，但产率较低，为 8-74%。所得四炔通过光谱方法和在某些情况下通过 X 射线晶体学进行表征。在 1-C8-1 和 3-C12-3 的情况下，对晶体数据的仔细分析显示出高度的碳链线性，% 收缩指数分别为
• 1-Iodobuta-1,3-diynes in Copper-Catalyzed Azide–Alkyne Cycloaddition: A One-Step Route to 4-Ethynyl-5-iodo-1,2,3-triazoles
  作者：Anastasia I. Govdi、Natalia A. Danilkina、Alexander V. Ponomarev、Irina A. Balova

  DOI：10.1021/acs.joc.8b02916

  日期：2019.2.15

  Cu-catalyzed 1,3-dipolar cycloaddition of iododiacetylenes with organic azides using iodotris(triphenylphosphine)copper(I) as a catalyst was found to be an efficient one-step synthetic route to 5-iodo-4-ethynyltriazoles. The reaction is tolerant to various functional groups in both butadiyne and azide moieties. The synthetic application of 5-iodo-4-ethynyl triazoles obtained was also evaluated: the

  发现使用碘化三（三苯基膦）铜（I）作为催化剂，将铜与有机叠氮化物催化碘代二乙炔与有机叠氮化物的1，3-偶极环加成反应是制备5-碘-4-乙炔基三唑的有效一步合成途径。该反应耐受丁二炔和叠氮化物部分中的各种官能团。还评估了所得的5-碘-4-乙炔基三唑的合成应用：Sonogashira与炔烃的偶联导致不对称取代的三唑稠合的二炔体系，而Suzuki反应产生了相应的5-芳基-4-乙炔基三唑。
• Cu-catalyzed cycloaddition of aryl azides to 1-iodobuta-1,3-diynes: an experimental and quantum chemical study of unusual regiochemistry
  作者：Anastasia I. Govdi、Natalia A. Danilkina、Andrey A. Shtyrov、Mikhail N. Ryazantsev、Mia D. Kim、Mariya A. Kryukova、Irina A. Balova

  DOI：10.1039/d3nj03823h

  日期：——

  regiochemistry of cycloaddition is determined by the type of azide N atom coordinated to the Cu atom and by a spatial arrangement of the binuclear Cu catalyst and alkyne in the TS. In particular in the case of 1-iodobuta-1,3-diynes both regioisomeric TSs have a linear orientation of the alkyne moiety and the I–Cu–P fragment of the binuclear catalyst that makes both N1–Cu (for 5-I-TS) and N3–Cu (for 4-I-TS)

  1-碘炔的铜催化叠氮-炔环加成（CuAAC）被称为 5-碘-1,2,3-三唑衍生物的合成工具。我们发现1-碘丁-1,3-二炔和芳基叠氮化物的CuAAC在CuI(PPh 3 ) 3催化下意外地导致4-碘-和5-碘-1,2,3-三唑的形成。带有受体基团的芳基叠氮化物和带有供体基团的碘代芳基二乙炔使异构体比例向有利于重要的4-碘三唑的方向转变。使用 DFT 计算解释了区域选择性变化的原因，该计算揭示了碘炔和叠氮化物环加成的 CuAAC 过渡态 (TS) 的双核性质。环加成的区域化学由与 Cu 原子配位的叠氮化物 N 原子的类型以及双核 Cu 催化剂和 TS 中炔烃的空间排列决定。特别是在 1-iodobuta-1,3-diynes 的情况下，两种区域异构 TS 都具有炔烃部分的线性取向和双核催化剂的 I-Cu-P 片段，使 N1-Cu（对于 5-I- TS) 和 N3-Cu (对于 4-I-TS)
• Synthesis, photophysics and excited state structure of 1,8-di(p-tolyl)-1,3,5,7-octatetrayne
  作者：I. Deperasińska、A. Szemik-Hojniak、K. Osowska、M.F. Rode、A. Szczepanik、Ł. Wiśniewski、T. Lis、S. Szafert

  DOI：10.1016/j.jphotochem.2010.10.023

  日期：2011.1

  The Cadiot-Chodkiewicz type C-2-elongation of p-tolylacetylene followed by dimerization of the resulted diyne p-CH3C6H4(C =C)(2)TMS (1) gave thermally stable octatetrayne p-CH3C6H4(C C)(4)-p-C6H4H3 (2) as light yellow powder in 75% yield. Compound 2 was characterized by spectroscopic methods and X-ray crystallography. Careful analysis of the crystal data revealed high degree of chain linearity with a potential for 1,n-topochemical polymerization. Next, photophysical properties of 2 were studied in details by experimental and advanced theoretical methods (ab initio HF as well as DFT calculations involving both the ground and excited state geometry optimization). These properties are similar to the properties of the parent polyyne C6H5(C C)(4)C6H5 previously described in literature (in particular, the lowest electronic excited singlet state (S-1) of 2 is a dark state). This was confirmed by the experimental facts, namely, few progressions of the stretching mode (a(g)) of the polyyne chain, starting from different "false origins" lying below the second excited (bright) state (S-2), were observed in the fluorescence excitation spectrum. The red shift of the electronic spectra (155 cm(-1) and 300 cm(-1) for absorption and fluorescence, respectively) and an increase of an energy gap between SI and 52 states by 450 cm(-1) are the effects of methylation of C6H5(C C)(4)C6H5 to 2. Theoretical results showed that in the excited state of 2 a shortening of single bonds and elongation of triple bonds occurred. This is in accordance with an observation of a long progression of the stretching vibration mode in the experimental absorption spectrum of 2. Besides that, stretching vibration of the polyyne chain is also active in the fluorescence spectra. (C) 2010 Elsevier B.V. All rights reserved.