2-N-piperidino-5-(2',2'-dicyanovinyl)thiophene | 344235-01-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-N-piperidino-5-(2',2'-dicyanovinyl)thiophene
• 英文别名: 2-(2-piperidino-5-thienylidene)malononitrile；2-N-piperidine-5-(2',2'-dicyanovinyl)thiophene；2-{[5-(piperidin-1-yl)thiophen-2-yl]methylene}malononitrile；TDCN；{[5-(Piperidin-1-yl)thiophen-2-yl]methylidene}propanedinitrile；2-[(5-piperidin-1-ylthiophen-2-yl)methylidene]propanedinitrile
• CAS: 344235-01-4
• 化学式: C₁₃H₁₃N₃S
• 分子量: 243.332
• InChiKey: FKYPGFMXLONMSE-UHFFFAOYSA-N

物化性质

• 沸点：
  447.2±45.0 °C(Predicted)
• 密度：
  1.246±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.384
• 拓扑面积：
  79.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  N-(2-噻吩基)哌啶 在 aluminum oxide 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 19.5h， 生成 2-N-piperidino-5-(2',2'-dicyanovinyl)thiophene
  参考文献：
  名称：

  丙二酸衍生物作为推挽分子中的电子吸收单元的职责

  摘要：

  以2-（N-哌啶基）噻吩中心供体为基础，制备了32种具有系统变化的丙二酸衍生的外周受体的模型推挽分子。通过修改π接头和结构排列（线性与四极D–π–A系统），可以实现进一步的性能调节。丙二酸衍生物，例如氰基乙酸，丙二酸，丙二酸二乙酯，Meldrum酸和N，N'-二丁基（硫代）巴比妥酸以及1，3-二酮类似物二甲酮和茚满-1，3-二酮被用作受体部分。Knoevenagel与四种噻吩醛的缩合反应以令人满意的产率提供了目标发色团。通过包括X射线分析，差示扫描量热法，电化学和UV / Vis吸收光谱的实验以及通过DFT计算来检查丙二酸受体的吸电子能力。结构-财产关系的细节已经阐明。根据增加的吸电子能力，广泛使用的丙二酸受体单元可以订购：丙二酸二乙酯≤氰基乙酸

  DOI：

  10.1002/ejoc.201700070

文献信息

• Synthesis and properties of novel second-order NLO chromophores containing pyrrole as an auxiliary electron donor
  作者：Xiaohua Ma、Ran Liang、Fan Yang、Zhenhua Zhao、Aixin Zhang、Naiheng Song、Qifeng Zhou、Jianping Zhang

  DOI：10.1039/b720023d

  日期：——

  A novel series of second-order NLO chromophores containing pyrrole as an auxiliary electron donor was synthesized via Knoevenagel reactions between 5-aminated N-methylpyrrole-2-carbaldehydes and different electron-accepting groups, i.e., malononitrile, picolinium tosylate and 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF). Their corresponding NLO chromophores containing thiophene in the place of pyrrole were also prepared for comparison. The resulting NLO chromophores showed good solubility in common organic solvents such as CHCl3, THF and DMF, except for TTCF containing thiophene and TCF, which is soluble in polar aprotic solvents but poorly soluble in less polar solvents. NMR studies of these chromophores showed that, in comparison with thiophene rings in the same type of NLO chromophores, pyrrole rings had higher electron density, as evidenced by the up-field chemical shifts of pyrrole protons. TGA investigations showed good thermal stability of these chromophores in nitrogen with the onset weight loss temperatures in the range of 203 to 296 °C. Positive solvatochromism of 10–44 nm from dioxane to chloroform were found for these chromophores, and moderate to very large molecular static hyperpolarizabilities (β0) of 57–1490 × 10−30 esu were revealed by hyper-Rayleigh scattering measurements. For chemical bonding to polymer chains, hydroxyl-containing NLO chromophores were also prepared and characterized for their linear and nonlinear optical properties.

  通过 5-氨基 N-甲基吡咯-2-羰基醛与不同电子接受基团（即丙二腈、吡啶对甲苯磺酸盐和 2-二氰基亚甲基-3-氰基-4,5,5-三甲基-2,5-二氢呋喃 (TCF)）之间的 Knoevenagel 反应，合成了一系列含有吡咯作为辅助电子供体的新型二阶 NLO 发色团。为了进行比较，还制备了含有噻吩而非吡咯的相应 NLO 发色团。所制备的 NLO 发色团在 CHCl3、THF 和 DMF 等常见有机溶剂中具有良好的溶解性，但含有噻吩的 TTCF 和 TCF 除外，它们在极性非丙烷溶剂中的溶解性较好，但在极性较弱的溶剂中的溶解性较差。对这些发色团进行的核磁共振研究表明，与同类 NLO 发色团中的噻吩环相比，吡咯环的电子密度更高，这一点可以从吡咯质子的上场化学位移得到证明。TGA 研究表明，这些发色团在氮气中具有良好的热稳定性，开始失重的温度在 203 至 296 °C 之间。通过超瑞利散射测量发现，这些发色团从二氧六环到氯仿的正溶解色度为 10-44 nm，分子静态超极化率（β0）为 57-1490 × 10-30 esu。为了与聚合物链进行化学键合，还制备了含羟基的 NLO 发色团，并对其线性和非线性光学特性进行了表征。
• The effect of the molecular structure of the chromophore on the photorefractive properties of the polymer systems with low glass transition temperatures
  作者：Hyunaee Chun、In Kyu Moon、Dong-Ho Shin、Sangyup Song、Nakjoong Kim

  DOI：10.1039/b105555k

  日期：2002.3.21

  Seven chromophores with different dipole moments and polarizability anisotropies were synthesized by varying conjugation bridges, such as polyene, thiophene, indole, and benzene combined with strong electron-donor and electron-acceptor groups. The birefringence of photorefractive materials containing 30 wt% of chromophore was observed to be in the range of 0.45 × 10−3 to 5.0 × 10−3 at an electric field of 70 V µm−1, depending on the chromophore structure. The photorefractive material containing a polyene-based chromophore exhibited the highest photorefractive property, followed by those containing thiophene-based, benzene-based and indole-based chromophores. It was observed that, within material systems used in this study, photorefractive properties of guest–host systems were linearly proportional to the orientational birefringence.

  通过不同的共轭桥，如多烯、噻吩、吲哚和苯，与强电子给体和电子受体基团结合，合成了七种具有不同偶极矩和极化各向异性的发色团。在 70 V µm−1 电场下，观察到含有 30 wt% 发色团的光折变材料的双折射率在 0.45 × 10−3 至 5.0 × 10−3 范围内，具体取决于发色团结构。含有多烯基发色团的光折变材料表现出最高的光折变性能，其次是含有噻吩基、苯基和吲哚基发色团的光折变材料。据观察，在本研究中使用的材料系统中，宾主系统的光折射特性与取向双折射成线性比例。
• Malonic Acid Derivatives on Duty as Electron-Withdrawing Units in Push-Pull Molecules
  作者：Milan Klikar、Veronika Jelínková、Zdeňka Růžičková、Tomáš Mikysek、Oldřich Pytela、Miroslav Ludwig、Filip Bureš

  DOI：10.1002/ejoc.201700070

  日期：2017.5.18

  molecules with systematically varied malonic acid-derived peripheral acceptors have been prepared. Further property tuning has been achieved by modifying the π-linker and the structural arrangement (linear vs. quadrupolar D–π–A systems). Malonic acid derivatives such as cyanoacetic acid, malondinitrile, diethyl malonate, Meldrum′s acid, and N,N′-dibutyl(thio)barbituric acid as well as 1,3-diketo analogues

  以2-（N-哌啶基）噻吩中心供体为基础，制备了32种具有系统变化的丙二酸衍生的外周受体的模型推挽分子。通过修改π接头和结构排列（线性与四极D–π–A系统），可以实现进一步的性能调节。丙二酸衍生物，例如氰基乙酸，丙二酸，丙二酸二乙酯，Meldrum酸和N，N'-二丁基（硫代）巴比妥酸以及1，3-二酮类似物二甲酮和茚满-1，3-二酮被用作受体部分。Knoevenagel与四种噻吩醛的缩合反应以令人满意的产率提供了目标发色团。通过包括X射线分析，差示扫描量热法，电化学和UV / Vis吸收光谱的实验以及通过DFT计算来检查丙二酸受体的吸电子能力。结构-财产关系的细节已经阐明。根据增加的吸电子能力，广泛使用的丙二酸受体单元可以订购：丙二酸二乙酯≤氰基乙酸