(E)-4-(2,6-di-tert-butyl-4H-pyran-4-ylidene)-but-2-enal | 1264135-64-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (E)-4-(2,6-di-tert-butyl-4H-pyran-4-ylidene)-but-2-enal
• 英文别名: 4-(2,6-di-tert-butyl-4H-pyran-4-ylidene)but-2-enal；(2E)-4-(2,6-di-tert-butyl-4H-pyran-4-ylidene)but-2-enal；(E)-4-(2,6-ditert-butylpyran-4-ylidene)but-2-enal
• CAS: 1264135-64-9
• 化学式: C₁₇H₂₄O₂
• 分子量: 260.376
• InChiKey: GSSATFQWVJQLDE-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-4-(2,6-di-tert-butyl-4H-pyran-4-ylidene)-but-2-enal 、 α-polyfunctional arylmethylenemalonitrile derivative 以 乙酸酐 为溶剂， 反应 1.0h， 以50%的产率得到(3Z,5E)-7-(2,6-di-tert-butyl-4H-pyran-4-ylidene)-2-phenylhepta-1,3,5-triene-1,13-tricarbonitrile
  参考文献：
  名称：

  4H-Pyran-4-ylidenes: Strong Proaromatic Donors for Organic Nonlinear Optical Chromophores

  摘要：

  Merocyanines where a polyenic spacer separates a 4H-pyran-4-ylidetic moiety and different strong organic acceptors have been synthesized. According to NMR studies and X-ray diffraction data, these compounds have weakly alternated structures and remarkably zwitterionic ground states, with a partial aromatic character that is compared to those of other pyran derivatives. The proaromaticity of the 4H-pyran-4-ylidene donor lies behind the cyanine-like behavior and low (positive or negative) second-order optical nonlinearities of the shorter derivatives. On the other hand, lengthening the pi-spacer gives rise to rapidly increasing mu beta(1907) values up to 17,400 x 10(-48) esu.

  DOI：

  10.1021/jo901142f
• 作为产物：
  描述：

  在 potassium hydroxide 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以205 mg的产率得到(E)-4-(2,6-di-tert-butyl-4H-pyran-4-ylidene)-but-2-enal
  参考文献：
  名称：

  4H-Pyran-4-ylidenes: Strong Proaromatic Donors for Organic Nonlinear Optical Chromophores

  摘要：

  Merocyanines where a polyenic spacer separates a 4H-pyran-4-ylidetic moiety and different strong organic acceptors have been synthesized. According to NMR studies and X-ray diffraction data, these compounds have weakly alternated structures and remarkably zwitterionic ground states, with a partial aromatic character that is compared to those of other pyran derivatives. The proaromaticity of the 4H-pyran-4-ylidene donor lies behind the cyanine-like behavior and low (positive or negative) second-order optical nonlinearities of the shorter derivatives. On the other hand, lengthening the pi-spacer gives rise to rapidly increasing mu beta(1907) values up to 17,400 x 10(-48) esu.

  DOI：

  10.1021/jo901142f

文献信息

• Aromatic/Proaromatic Donors in 2-Dicyanomethylenethiazole Merocyanines: From Neutral to Strongly Zwitterionic Nonlinear Optical Chromophores
  作者：Raquel Andreu、Elena Galán、Jesús Orduna、Belén Villacampa、Raquel Alicante、Juan T. López Navarrete、Juan Casado、Javier Garín

  DOI：10.1002/chem.201002158

  日期：2011.1.17

  whereas 4H‐pyran‐4‐ylidene‐ and 4‐pyridylidene‐containing compounds are zwitterionic and 1,3‐dithiol‐2‐ylidene derivatives are close to the cyanine limit, anilino‐derived merocyanines are essentially neutral. This very large range of intramolecular charge transfer (ICT) gives rise to efficient second‐order NLO chromophores with μβ values ranging from strongly negative to strongly positive. In particular

  制备了推挽式化合物，其中一个芳香族电子供体与一个2-二氰基亚甲基噻唑受体结合。与具有芳香族供体的模型化合物相比，它们的性能更佳。结合实验（X射线衍射，1 H NMR，IR，拉曼，UV / Vis，非线性光学（NLO）测量）和理论研究表明，结构和溶剂效应决定了这些花菁的基态极化：而4 H含吡喃-4-亚烷基和4-吡啶亚基的化合物为两性离子型，1,3-二硫醇-2-亚烷基衍生物接近花青的限度，苯胺衍生的花菁本质上是中性的。分子内电荷转移（ICT）的范围非常广，可产生高效的二阶NLO生色团μβ值的范围从强负到强正。尤其是，吡喃亚烷基衍生物不寻常，因为它们在加长π间隔物时显示出ICT程度的提高，而该特征在于它们显示出的非常大的负μβ值。将形式为喹啉的2-二氰基亚甲基噻唑部分与原芳香族供体连接起来似乎是优化两性离子NLO发色团的一种有前途的方法。
• Conformational analysis of polymethine dyes derived from the 2-azaazulene
  作者：Aleksey B. Ryabitskii、Julia L. Bricks、Aleksey D. Kachkovskii、Vladimir V. Kurdyukov

  DOI：10.1016/j.molstruc.2011.10.003

  日期：2012.1

  Abstract A systematic investigation of the conformational structure was performed for the series of symmetrical and unsymmetrical mono-, tri-, pentamethine cyanines, and styryl dyes bearing 2-azaazulenium terminal group. The rotation energy barriers of terminal groups were determined via the dynamic variable temperature NMR experiments. The conformational transformation energy was calculated by quantum

  摘要 系统研究了一系列对称和不对称的单、三、五次甲基花青和带有 2-氮杂azulenium 端基的苯乙烯基染料的构象结构。末端基团的旋转能垒是通过动态变温核磁共振实验确定的。在考虑溶剂影响和不考虑溶剂影响的情况下，通过量子化学方法（B3LYP 和 M05-2X）计算了构象转换能。基于理论和实验数据的比较，估计了2-氮杂氮杂染料中杂环端基的相对给电子能力和几何特征。通过考虑动态核磁共振研究的结果，提出了某些杂环核按碱度排列的顺序。讨论了共轭链长和溶剂性质对所研究染料分子构象不稳定性的影响。
• Polarization, second-order nonlinear optical properties and electrochromism in 4H-pyranylidene chromophores with a quinoid/aromatic thiophene ring bridge
  作者：A. Belén Marco、Paula Mayorga Burrezo、Laura Mosteo、Santiago Franco、Javier Garín、Jesús Orduna、Beatriz E. Diosdado、Belén Villacampa、Juan T. López Navarrete、Juan Casado、Raquel Andreu

  DOI：10.1039/c4ra12791a

  日期：——

  between compounds that only differ in the character (quinoid or aromatic) of the thiophene unit shows a more efficient ICT for the quinoid thiophene-containing chromophore, which influences the second-order NLO response. Furthermore, the thienyl ring has been also found to play a significant role in the ICT process for the analogous aromatic derivative.

  制备了推挽系统，其中原芳香族的4 H-吡喃亚基电子供体通过作为电子继电器的一部分的喹啉噻吩与二氰基亚甲基受体共轭，并且已将其性能与母体化合物的性能进行了比较。具有芳族噻吩部分。不同的实验技术（X射线衍射，1 H NMR，IR，拉曼，紫外可见，循环伏安法，光谱电化学和NLO测量）与理论计算相结合已用于发色团的研究。quinoidal衍生物虽然是中性的，但显示出强烈的极化结构，具有正的μβ值和分子内电荷转移（ICT）在加长π间隔物时逐渐增加。仅在噻吩单元的特征（喹啉或芳族）方面不同的化合物之间的比较显示，含醌噻吩的生色团的信息通信技术效率更高，这会影响二阶NLO反应。此外，还发现噻吩基环在ICT过程中对于类似的芳族衍生物起着重要的作用。
• D−π–A Compounds with Tunable Intramolecular Charge Transfer Achieved by Incorporation of Butenolide Nitriles as Acceptor Moieties
  作者：Carlos Moreno-Yruela、Javier Garín、Jesús Orduna、Santiago Franco、Estefanía Quintero、Juan T. López Navarrete、Beatriz E. Diosdado、Belén Villacampa、Juan Casado、Raquel Andreu

  DOI：10.1021/acs.joc.5b02051

  日期：2015.12.18

  Chromophores where a polyenic spacer separates a 4H-pyranylidene or benzothiazolylidene donor and three different butenolide nitriles have been synthesized and characterized. The role of 2(5H)-furanones as acceptor units on the polarization and the second-order nonlinear (NLO) properties has been studied Thus, their incorporation gives rise to moderately polarized structures with NLO responses that compare favorably to those of related compounds featuring more efficient electron-withdrawing moieties. Derivatives of the proaromatic butenolide PhFu show the best nonlinearities. Benzothiazolylidene-containing chromophores present less alternated structures than their pyranylidene analogues, and, unlike most merocyanines, the degree of charge transfer does not decrease on lengthening the pi-bridge.
• Linear and V-Shaped Nonlinear Optical Chromophores with Multiple 4<i>H</i>-Pyran-4-ylidene Moieties
  作者：Raquel Andreu、Elena Galán、Javier Garín、Vanessa Herrero、Edurne Lacarra、Jesús Orduna、Raquel Alicante、Belén Villacampa

  DOI：10.1021/jo902670z

  日期：2010.3.5

  A simple synthesis of dipolar one- and two-dimensional chromophores bearing two or three 4H-pyran-4-ylidene moieties is reported. Whereas the pyranylidene fragments acting as donors are proaromatic, the spacer one is not. In the linear derivatives, Chain elongation gives rise to a sharp increase in the second order nonlinear optical responses, but some V-shaped derivatives display first hyperpolarizabilities (beta) lower than those of their linear analogues. This uncommon feature lends experimental support to previous theoretical studies on the relative contribution and sign of the beta-tensor components.