2-[4,5-bis(methylthio)-1,3-dithiole-2-ylidene]-(1,3)-dithiolo[4,5-c]pyrrole | 250687-34-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-[4,5-bis(methylthio)-1,3-dithiole-2-ylidene]-(1,3)-dithiolo[4,5-c]pyrrole
• 英文别名: 2-{4,5-bis(methylthio)-1,3-dithiol-2-ylidene}-[1,3]dithiolo[4,5-c]pyrrole；mono(pyrrolo)tetrathiafulvalene；2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-5H-[1,3]dithiolo[4,5-c]pyrrole
• CAS: 250687-34-4
• 化学式: C₁₀H₉NS₆
• 分子量: 335.584
• InChiKey: BEAOUROGPJGMHW-UHFFFAOYSA-N

物化性质

• 熔点：
  143.5-144 °C (decomp)
• 沸点：
  401.6±45.0 °C(Predicted)
• 密度：
  1.67±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  168
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-[4,5-bis(methylthio)-1,3-dithiole-2-ylidene]-(1,3)-dithiolo[4,5-c]pyrrole 在 sodium hydride 、 溶剂黄146 、 三氯氧磷 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 52.0h， 生成
  参考文献：
  名称：

  具有基于单吡咯并四硫富富烯烯单元的有机胶的聚（芳醚）树枝状分子，具有凝胶诱导的增强发射（GIEE）

  摘要：

  设计并合成了一系列通过酰基键连接的具有单吡咯并四硫富瓦烯单元的聚（芳基醚）树突，作为低分子量有机胶凝剂（LMOG）。两个树枝状分子可以使芳族溶剂和某些溶剂混合物胶凝，但是其他的则不能使除正戊醇以外的所有测试溶剂胶凝。分子结构的细微变化对胶凝行为产生很大影响。请注意，树枝状分子无需加热即可在DMSO /水混合物中形成稳定的凝胶，还可以与富勒烯形成二元凝胶（C 60）在甲苯中。形成的凝胶在暴露于外部刺激（例如温度和化学氧化/还原）时会经历可逆的凝胶-溶胶相变。大量实验（SEM，FTIR光谱，11 H NMR光谱，UV / Vis吸收光谱和XRD）表明，这些树枝状分子自组装成弹性互穿的一维纤维状聚集体，并在有机凝胶中保持矩形分子堆积模式。发现氢键，π-π和供体-受体相互作用是形成凝胶的主要驱动力。此外，尽管不存在常规的荧光团单元，但该凝胶体系仍在可见光区域表现出凝胶诱导的增强发射（GIEE）特性，并且通过引入C

  DOI：

  10.1002/chem.201502044
• 作为产物：
  描述：

  在 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 0.83h， 生成 2-[4,5-bis(methylthio)-1,3-dithiole-2-ylidene]-(1,3)-dithiolo[4,5-c]pyrrole
  参考文献：
  名称：

  Pyrrolo-Annelated Tetrathiafulvalenes:  The Parent Systems

  摘要：

  The synthesis of a number pyrrolo-annelated tetrathiafulvalenes, including the parent bis(pyrrolo-[3,4-d])tetrathiafulvalene (7) is decribed. Starting from readily available 4,5-bis(bromomethyl)-1,3-dithiole-2-thione (14) and sodium tosylamide, the parent 7 and the asymmetric monopyrrolo tetrathiafulvalenes 23a;b were prepared in good yields via a nonclassical and simple pyrrole synthesis. Furthermore, a series of asymmetrical N-alkylated monopyrrolo/monodihydropyrrolotetrathiafulvalenes was prepared starting from primary amines and 14. A detailed study of the fundamental redox behavior of this class of heterocycles is reported. NMR spectroscopy, cyclic voltammetry, and PM3 MO calculations revealed that the pyrrolo-annelated tetrathiafulvalenes have highly extended pi-surfaces. The X-ray crystallographic analyses of the monopyrrolo tetrathiafulvalenes 22b and 24b, together with preliminary formation of a charge-transfer complex between the parent donor 7 and TCNQ, are also reported.

  DOI：

  10.1021/jo000742a

文献信息

• Tuning of tetrathiafulvalene properties: versatile synthesis of <i>N</i>-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions
  作者：Vladimir A Azov、Diana Janott、Dirk Schlüter、Matthias Zeller

  DOI：10.3762/bjoc.11.96

  日期：——

  Ullmann-type coupling reaction was employed for the preparation of several N-arylated monopyrrolotetrathiafulvalenes with variable substitution patterns. Spectroscopic and electrochemical properties of the coupling products strongly depend on the electronic nature of the aromatic substituents due to their direct conjugation with the tetrathiafulvalene chromophore. The crystal packing of the arylated

  乌尔曼型偶联反应用于制备几种具有可变取代模式的N-芳基单吡咯并四硫富瓦烯。偶联产物的光谱和电化学性质在很大程度上取决于芳族取代基的电子性质，因为它们与四硫富瓦烯生色团直接共轭。芳基化的单吡咯并四硫富瓦烯的晶体堆积主要由CH ... X弱氢键和涉及四硫富瓦烯部分的短S ... S接触网络组成。
• Self‐Assembled Cages from the Electroactive Bis(pyrrolo)tetrathiafulvalene (BPTTF) Building Block
  作者：Sébastien Bivaud、Sébastien Goeb、Jean‐Yves Balandier、Marcos Chas、Magali Allain、Marc Sallé

  DOI：10.1002/ejic.201400060

  日期：2014.5

  including UV/Vis spectrometry and cyclic voltammetry studies, X-ray diffraction on single crystals, and DFT calculations. A significant degree of conjugation between the π-donating bis(pyrrolo)tetrathiafulvalene (BPTTF) and the electron-withdrawing coordinating pyridyl units is observed. The tetrapyridyl ligand is able to self-assemble in the presence of cis-protected PtII complexes to produce the first

  描述了设计用于生成离散自组装金属熔体的一系列二元和四元氧化还原活性配体，包括紫外/可见光谱和循环伏安法研究、单晶 X 射线衍射和 DFT 计算。观察到 π 供体双（吡咯并）四硫富瓦烯（BPTTF）和吸电子配位吡啶基单元之间存在显着程度的共轭。四吡啶基配体能够在顺式保护的 PtII 复合物存在下自组装，以产生基于 BPTTF 的笼子的第一个例子，该笼子具有易于封装客体的空腔。这些金属溶胶在 DMSO 中加热后会发生最初的化学转化，得到 Pt-二硫烯配合物，其中之一通过 XRD 进行表征。该反应可以扩展到替代的 BPTTF 衍生物。
• Honing Up a Genre of Amphiphilic Bistable [2]Rotaxanes for Device Settings
  作者：Jan�O. Jeppesen、Sune Nygaard、Scott�A. Vignon、J.�Fraser Stoddart

  DOI：10.1002/ejoc.200400530

  日期：2005.1

  tetracationic cyclophane, cyclobis(paraquat-p-phenylene), to reside around. In contrast to a previously reported “slow” amphiphilic bistable [2]rotaxane, which has an SMe group attached directly to the (monopyrrolo)tetrathiafulvalene unit, this “new and improved” bistable [2]rotaxane has a much less bulky hydrogen atom attached to the (monopyrrolo)tetrathiafulvalene unit. This seemingly small difference in

  为了响应分子电活性器件的要求，设计、合成和表征了两亲双稳态 [2] 轮烷形状的分子穿梭机。它包含一个疏水的四芳基甲烷和一个亲水的树枝状塞子和两个富含 π 电子的站——一个（单吡咯）四硫富瓦烯单元和一个 1,5-二氧萘部分——位于其哑铃部件的杆部分，可以作为识别四阳离子环芳环双（百草枯-对亚苯基）的位置。与先前报道的“慢速”两亲双稳态 [2] 轮烷相比，后者具有直接连接到（单吡咯并）四硫富瓦烯单元的 SMe 基团，这种“新的和改进的”双稳态 [2] 轮烷所连接的氢原子体积要小得多到（单吡咯）四硫富瓦烯单元。在比较两种双稳态 [2] 轮烷的物理性质时，（单吡咯并）四硫富瓦烯单元上取代基的这种看似微小的差异导致了深刻的变化。还制备了两种仅包含（单吡咯并）四硫富瓦烯单元的亲水性半哑铃化合物和一种仅在其杆部分包含 1,5-二氧萘部分的疏水性半哑铃化合物，并用于形成它们相应的环双（百草枯-对亚苯基）复合体。已经使用吸收和
• WO2007/132430
  申请人：——

  公开号：——

  公开（公告）日：——
• Binding Studies between Triethylene Glycol-Substituted Monopyrrolotetrathiafulvalene Derivatives and Cyclobis(paraquat-<i>p</i>-phenylene)
  作者：Sune Nygaard、Camilla N. Hansen、Jan O. Jeppesen

  DOI：10.1021/jo061962c

  日期：2007.3.1

  The synthesis of several pi-electron-donating monopyrrolotetrathiafulvalene (MPTTF) derivatives, which conceptually can be divided into three classes containing none, one, or two triethylene glycol (TEG) substituents, is described. In all cases, the complexation between the pi-electron donating MPTTF unit and the pi-electron-deficient tetracationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT(4+)) has been investigated using UV-vis dilution techniques. The results reveal that the strength of the binding between MPTTF derivatives and CBPQT(4+) is directly correlated to the pi-electron donating properties of the MPTTF derivatives. However, the pi-electron-donating properties of the MPTTF derivatives is not the only factor of importance. The results enclosed in the present studies demonstrate that the TEG substituents assist the complexation process most likely on account of their capacity to participate in [C-H center dot center dot center dot O] hydrogen bonding interactions with some of the alpha-CH protons in the bipyridinium units of CBPQT(4+) and the stabilizing effect that attachment of one or two TEG substituents to the MPTTF unit exerts upon complexation with CBPQT(4+) has been quantified to approximately 0.3 and 0.5 kcal mol(-1), respectively. These results serve to lay an extended foundation for the understanding of which buttons to push when it comes to improve the design of bistable molecular switches based on (MP)TTF and CBPQT(4+).