methyl 5-mercapto-2-thioxo-1,3-dithiole-4-carboxylate | 146581-51-3

• 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: methyl 5-mercapto-2-thioxo-1,3-dithiole-4-carboxylate
• 英文别名: 4-mercapto-5-methoxycarbonyl-1,3-dithiole-2-thione；5-methoxycarbonyl-4-mercapto-1,3-dithiole-2-thione；4-Mercapto-5-carbomethoxy-1,3-dithiole-2-thione；4-Mercapto-5-methoxycarbonyl-1,3-dithiol-2-thione；methyl 5-sulfanyl-2-sulfanylidene-1,3-dithiole-4-carboxylate
• CAS: 146581-51-3
• 化学式: C₅H₄O₂S₄
• 分子量: 224.35
• InChiKey: RHUXRERXLSRRKU-UHFFFAOYSA-N

物化性质

• 沸点：
  329.6±52.0 °C(Predicted)
• 密度：
  1.63±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 5-mercapto-2-thioxo-1,3-dithiole-4-carboxylate 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 氯仿 为溶剂， 反应 7.0h， 生成
  参考文献：
  名称：

  Synthesis and properties of new bridged tetrathiafulvalenes

  摘要：

  The condensation reaction of dithiole phosphonium perchlorates 17 and 18a-c with 2-ethylselenodithiolium tetrafluoroborate 16 in the presence of triethylamine was employed for the high-yield synthesis of four new donors 7a-c, 9 of the tetrathiafulvalene series. The carbomethoxy groups of 7a-c were removed by basic hydrolysis followed by decarboxylation to give 8a-c. Electrochemical studies for seven new TTFs were carried out. An unusual effect resulting in an decrease of the first oxidation potential was observed for 7b. Some properties of the starting 4-mercapto-5-carbomethoxy-1,3-dithiole-2-thione (10) are reported.

  DOI：

  10.1021/jo00058a012
• 作为产物：
  描述：

  二硫化碳 、 O-methyl S-(methoxycarbonylmethyl)dithiocarbonate 在 sodium t-butanolate 作用下， 反应 2.0h， 以62%的产率得到methyl 5-mercapto-2-thioxo-1,3-dithiole-4-carboxylate
  参考文献：
  名称：

  Synthesis and properties of new bridged tetrathiafulvalenes

  摘要：

  The condensation reaction of dithiole phosphonium perchlorates 17 and 18a-c with 2-ethylselenodithiolium tetrafluoroborate 16 in the presence of triethylamine was employed for the high-yield synthesis of four new donors 7a-c, 9 of the tetrathiafulvalene series. The carbomethoxy groups of 7a-c were removed by basic hydrolysis followed by decarboxylation to give 8a-c. Electrochemical studies for seven new TTFs were carried out. An unusual effect resulting in an decrease of the first oxidation potential was observed for 7b. Some properties of the starting 4-mercapto-5-carbomethoxy-1,3-dithiole-2-thione (10) are reported.

  DOI：

  10.1021/jo00058a012

文献信息

• New bi(tetrathiafulvalenyl) derivatives and their radical cations: synthetic and X-ray structural studies
  作者：Derek E. John、Adrian J. Moore、Martin R. Bryce、Andrei S. Batsanov、Michael A. Leech、Judith A. K. Howard

  DOI：10.1039/b000790k

  日期：——

  A series of bi(tetrathiafulvalenyl) derivatives has been prepared from iodo-TTF precursors by Ullmann coupling (copper in refluxing N,N-dimethylformamide) or by reaction with copper(I) thiophene-2-carboxylate (CuTC) in 1-methylpyrrolidin-2-one at 20 °C. Solution electrochemical and UV-VIS spectroscopic studies suggest that there is no significant through-bond interaction between the two TTF units in these systems. The X-ray crystal structures are reported for 4,5,5′,5′′,4′′′,5′′′-hexakis(methylsulfanyl)-4′,4′′-bitetrathiafulvalene 9 and a semiconducting 1∶1 perchlorate salt of 4,5:4′′′,5′′′-bis(ethylenedithio)-5′,5′′-dimethyl-4′,4′′-bitetrathiafulvalene 8+··ClO4−. The torsion angle around the central bond is 89° in 9 and 77° in 8+··ClO4−. The crystal packing of 8+··ClO4− is characterised by puckered layers, parallel to the (001) plane, of cations contacting via their sulfur atoms; the anions occupy infinite channels, parallel to the z-axis and running through the cation motif.

  一系列双（四硫富瓦烯基）衍生物已通过Ullmann偶联反应（在回流的N,N-二甲基甲酰胺中使用铜）或通过在20°C下与铜（I）噻吩-2-羧酸盐（CuTC）在1-甲基吡咯烷-2-酮中反应，从碘代TTF前体制备得到。溶液电化学和UV-VIS光谱学研究表明，在这些体系中，两个TTF单元之间没有显著的键间相互作用。报道了4,5,5',5'',4''',5'''-六甲硫基-4',4''-双四硫富瓦烯9和4,5:4''',5'''-双（乙二硫基）-5',5''-二甲基-4',4''-双四硫富瓦烯8+··ClO4−的1∶1高氯酸盐半导体的X射线晶体结构。在9中，中心键的扭转角度为89°，在8+·· −中为77°。8+·· −的晶体堆积特征为通过硫原子接触的阳离子形成的褶皱层，平行于（001）平面；阴离子位于平行于z轴并穿过阳离子图案的无穷通道中。
• Two Isomeric Triple-Layered Tetrathiafulvalenophanes: Syntheses, Structures, and Electrochemical Properties
  作者：Shin-ichi Yunoki、Kazuo Takimiya、Yoshio Aso、Tetsuo Otsubo*

  DOI：10.1016/s0040-4039(97)00523-6

  日期：1997.4

  The first triple-layered tetrathiafulvalenophanes of two different stacking types have been synthesized and characterized with cyclic voltammetry. In addition, the structure of an isomer of the parallel-oriented type was elucidated by an X-ray crystal analysis. © 1997 Elsevier Science Ltd.

  合成了两种不同堆叠类型的第一批三层四硫富瓦戊烯，并用循环伏安法进行了表征。另外，通过X射线晶体分析阐明了平行取向型异构体的结构。©1997爱思唯尔科学有限公司。
• Synthesis and Properties of Higher-Order Tetrathiafulvalene Oligomers up to the Dodecamer
  作者：Tadashi Kageyama、Shinpei Ueno、Kazuo Takimiya、Yoshio Aso、Tetsuo Otsubo

  DOI：10.1002/1099-0690(200108)2001:15<2983::aid-ejoc2983>3.0.co;2-6

  日期：2001.8

  A series of TTF oligomers, the monomer (1), the dimer (2), the trimer (3), the tetramer (4), the hexamer (5), the octamer (6), the decamer (7), and the dodecamer (8) has been synthesized as novel electrooptical materials. Their structures were well characterized by MS and NMR spectroscopy. GPC measurements indicated that they have extended structures, with the increasing number of TTF units, but comprised

  一系列TTF低聚物，单体（1）、二聚体（2）、三聚体（3）、四聚体（4）、六聚体（5）、八聚体（6）、十聚体（7）和十二聚体 (8) 已被合成为新型电光材料。它们的结构通过 MS 和 NMR 光谱进行了充分表征。GPC 测量表明它们具有扩展的结构，随着 TTF 单元数量的增加，但由于 E/Z 构象而包含各种异构体混合物。循环伏安研究表明，这些低聚物是高度多重氧化还原系统，特别是最高的十二聚体表现出可逆的、结构较少的氧化还原波，涉及 24 个电子氧化步骤。十二聚体的旋涂膜表现出黄色、黄绿色和蓝色的电致变色，这是由于中性、自由基阳离子，
• Synthesis of linear oligo-TTFs and their [2]rotaxanes with cyclobis(paraquat-p-phenylene)
  作者：Dorthe Damgaard、Mogens Brøndsted Nielsen、Jesper Lau、Kenneth Bendix Jensen、Roman Zubarev、Eric Levillain、Jan Becher

  DOI：10.1039/b001868f

  日期：——

  Two linear oligo-TTFs were synthesised employing a stepwise strategy involving two different thiolate protecting groups. These linear TTFs were incorporated into donor–acceptor rotaxanes with the cyclic acceptor, cyclobis(paraquat-p-phenylene). Moreover, a prototype rotaxane based on a bis(pyrrolo)-TTF was prepared and studied.

  采用涉及两种不同硫醇酯保护基团的分步策略，合成了两种线性寡 TTF。这些线性 TTF 与环状受体环双（百草枯对苯二甲酸酯）结合成了供体-受体轮烷。此外，还制备并研究了一种基于双（吡咯）-TTF 的轮烷原型。