4,5-bis(bromomethyl)-1,3-dithiol-2-one | 153911-38-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 4,5-bis(bromomethyl)-1,3-dithiol-2-one
• CAS: 153911-38-7
• 化学式: C₅H₄Br₂OS₂
• 分子量: 304.026
• InChiKey: QRVPOZWYPXKOSU-UHFFFAOYSA-N

物化性质

• 沸点：
  343.2±52.0 °C(Predicted)
• 密度：
  2.141±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,5-bis(bromomethyl)-1,3-dithiol-2-one 在 sodium methylate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 氯苯 为溶剂， 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：

  四硫富瓦烯性质的调节：N-芳基化的单吡咯并四硫富瓦烯通过乌尔曼型偶联反应的多功能合成。

  摘要：

  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。

  DOI：

  10.3762/bjoc.11.96
• 作为产物：
  描述：

  4,5-dimethyl-1,3-dithiol-2-one 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 反应 4.5h， 以58%的产率得到4,5-bis(bromomethyl)-1,3-dithiol-2-one
  参考文献：
  名称：

  Improved Synthesis of the High-Mobility Organic Semiconductor Dithio­phene-Tetrathiafulvalene

  摘要：

  二噻吩-四硫杂戊烯（DT-TTF）已被证明是一种很有前途的有机半导体，可用于有机晶体管，因为它兼具高迁移率和可加工性。本文介绍了制备这种材料的新型合成方法。它涉及 1,3-二硫醇-2-酮的偶联。该方法的产率高于之前报道的产率。

  DOI：

  10.1055/s-2007-966053

文献信息

• CpCo^I-mediated Diels–Alder Reaction Forming Dimeric 1,3-Dithiol-2-one Derivative with Spiro Structure and Successive Formation of Novel Cobalt Dithiolene Complex
  作者：Tatsuya Masui、Mitsushiro Nomura、Yusuke Kobayashi、Kosuke Terada、Chikako Fujita-Takayama、Toru Sugiyama、Masatsugu Kajitani

  DOI：10.1246/cl.2008.1032

  日期：2008.10.5

  4,5-Bis(bromomethyl)-1,3-dithiol-2-one (1) reacts with CpCo(CO) 2 (2) under thermal condition to undergo a debromination of 1 and to form dimeric 1,3-dithiol-2-one derivative having a spiro structure 3 by the [4 + 2] Diels-Alder reaction, and the resulted 3 further reacts with 2 to afford new CpCo-(dithiolene) complex 4.

  4,5-Bis(bromomethyl)-1,3-dithiol-2-one (1) 在热条件下与 CpCo(CO) 2 (2) 反应以进行 1 的脱溴并形成二聚体 1,3-dithiol-通过[4 + 2] Diels-Alder反应生成具有螺结构3的2-一衍生物，所得3进一步与2反应得到新的CpCo-(二硫烯)配合物4。
• Tripodal pyrrolotetrathiafulvalene receptors for recognition of electron-deficient molecular guests
  作者：Michèle-Laure Lieunang Watat、Thomas Dülcks、Dorit Kemken、Vladimir A. Azov

  DOI：10.1016/j.tetlet.2013.12.011

  日期：2014.1

  We report the synthesis of tripodal receptors with monopyrrolo-tetrathiafulvalene arms 1a,b, based on 1,3,5-substituted 2,4,6-triethylbenzene scaffold. The three converging pyrrolotetrathiafulvalene groups form an electron rich cone-shaped binding site. Molecular hosts 1a,b are capable of binding neutral electron deficient guests in solution, as well as positively charged pyridinium species in the

  我们报道了基于1,3,5-取代的2,4,6-三乙苯支架的单吡咯并四硫富瓦烯臂1a，b的三脚架受体的合成。三个会聚的吡咯并四硫富瓦烯基形成富电子的锥形结合位点。分子主体1a，b能够结合溶液中的中性电子不足的来宾以及气相中带正电的吡啶鎓类物质。
• Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units
  作者：David Kreher、Michel Cariou、Sheng-Gao Liu、Eric Levillain、Jaume Veciana、Concepció Rovira、Alain Gorgues、Piétrick Hudhomme

  DOI：10.1039/b201695h

  日期：2002.6.21

  Our recent works on fused TTF–C60 dyads, (TTF)n–C60 polyads and C60–TTF–C60 dumbbell triads in which the acceptor C60 is doubly tethered to the donor tetrathiafulvalene through a rigidified cyclohexene ring are presented. This approach was developed in order to control the relative orientation as well as the distance between both donor and acceptor entities. Thereby, through-space interactions which are of great importance for photoinduced electron- and/or energy-transfer processes are expected to dominate because of the special topology of the molecules. The two linked C60 and TTF chromophores in such adducts are not only in close proximity but also have optimal orbital orientations, thus facilitating these through-space electronic interactions. These new C60-based assemblies were synthesized by [4 + 2] Diels–Alder cycloaddition reactions. The different methodologies considered for their synthesis are discussed, their analytical, spectroscopic characterizations and electrochemical properties are also described. The selective electro-oxidation or reduction afforded the corresponding radical cation and radical anion which were characterized by EPR. These C60-based assemblies were studied for their nonlinear optical and optical limiting applications. Moreover, intramolecular photoinduced charge-separation and charge-recombination processes in a fused C60–TTF–C60 dumbbell triad which was designed to be soluble in organic solvents were investigated by time-resolved absorption and fluorescence techniques. Appreciable interaction between the C60 moiety and TTF moiety in the ground state was suggested by steady-state absorption spectra and the fluorescence spectra showed considerable interaction in the singlet excited state. The nanosecond transient absorption spectra displayed the formation of the charge-separated radical pair C60–TTF˙+–C60˙−, characterized by a lifetime of ca. 20 ns in benzonitrile.

  我们最近的研究工作集中在融合的TTF–C60二聚体、(TTF)n–C60多聚体和C60–TTF–C60哑铃三聚体，这些体系中受体C60通过刚性的环己烯环与供体四硫富瓦烯双重连接。此方法的开发旨在控制供体和受体之间的相对方向和距离。因此，由于分子的特殊拓扑结构，空间内的相互作用在光诱导电子及/或能量转移过程中预计将占主导地位。这种加合物中连接的C60和TTF色团不仅相互接近，而且具有最佳的轨道取向，从而促进这些跨空间的电子相互作用。这些新的基于C60的组装体是通过[4 + 2]迪尔斯－阿尔德环加成反应合成的。文中讨论了其合成过程中考虑的不同方法，并描述了它们的分析、光谱特性及电化学性质。选择性电氧化或还原生成了相应的自由基阳离子和自由基阴离子，这些都通过电子顺磁共振（EPR）进行了表征。这些基于C60的组装体也被研究用于其非线性光学和光限制应用。此外，设计为可溶于有机溶剂的融合C60–TTF–C60哑铃三聚体中的分子内光诱导电荷分离和电荷重组过程通过时间分辨吸收和荧光技术进行了研究。在基态中，稳态吸收光谱表明C60基团与TTF基团之间存在显著的相互作用，而荧光光谱则显示在单重激发态中也存在较强的相互作用。纳秒瞬态吸收光谱显示了电荷分离的自由基对C60–TTF˙+–C60˙–，其在苯腈中表征的寿命约为20纳秒。
• Lower‐Rim‐Modified Calix[4]arene‐Pyrrolotetrathiafulvalene Molecular Tweezers
  作者：Dirk Schlüter、Kai R. Korsching、Vladimir A. Azov

  DOI：10.1002/ejoc.202100676

  日期：2021.8.20

  Calix[4]arene-tetrathiafulvalene molecular tweezers modified on the lower rim were synthesized using an Ullman coupling–click reaction sequence.

  下缘修饰的杯[4]芳烃-四硫富瓦烯分子镊子使用Ullman偶联-点击反应序列合成。
• A new promising π-donor of the tetrathiafulvalene series: bis(2,3-dithiabutane-1,4-diyl)tetrathiafulvalene, the symmetrical outer S-position isomer of BEDT-TTF
  作者：C. Durand、P. Hudhomme、G. Duguay、C. Durand、M. Jubault、A. Gorgues

  DOI：10.1039/a707486g

  日期：——

  New functionalities are introduced into the 2-(thi)oxo-1,3-dithiole system and applied to the synthesis of the title compound.

  在 2-(噻)氧代-1,3-二硫杂环系统中引入了新的官能团，并将其用于合成标题化合物。