4,5-bis(cyanoethylthio)-1,3-dithiole-2-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene] | 158871-27-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 英文名称: 4,5-bis(cyanoethylthio)-1,3-dithiole-2-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene]
• 英文别名: 4,5-bis[(2-cyanoethyl)thio]-4',5'-ethylenedithiotetrathiafulvalene；2,3-bis(2-cyanoethylthio)-6,7-ethylenedithiotetrathiafulvalene；4,5-bis(2′-cyanoethylthio)-4′,5′-ethylenedithiotetrathiafulvalene；3,3'-[[2-(5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-dithiole-4,5-diyl]bis(thio)]bis[propanenitrile]；4,5-bis(cyanoethylthio)-1,3-dithole-2-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene]；2,3-bis(2-cyanoethylthio)-6,7-(1,4-dithiabutan-1,4-diyl)-1,4,5,8-tetrathiafulvalene；4,5-bis(cyanoethylthio)-1,3-dithiole-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene]；4,5-bis(cyanoethylthio)-1,3-dithiole-[(4,5-ethylenedithio)-1,3-dithione-2-ylidene]；3-[[5-(2-Cyanoethylsulfanyl)-2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 158871-27-3
• 化学式: C₁₄H₁₂N₂S₈
• 分子量: 464.791
• InChiKey: VFEBMDPOKOJICW-UHFFFAOYSA-N

物化性质

• 熔点：
  141 °C(Solv: chloroform (67-66-3); methanol (67-56-1))
• 沸点：
  602.2±55.0 °C(Predicted)
• 密度：
  1.65±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  250
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  4,5-bis(cyanoethylthio)-1,3-dithiole-2-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene] 在 cesium hydroxide 、 四丁基溴化铵 、 zinc(II) chloride 作用下， 生成 5-(4,5-ethylenedilthio-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalen-2-one
  参考文献：
  名称：

  Conducting Salts Composed of Selenium Analogues of TMET-TTP

  摘要：

  TMET-TTP（2-(4,5-双硫甲基-1,3-二硫杂环-2-亚基)-5-(4,5-乙烯基二硫-1,3-二硫杂环-2-亚基)-1,3,4,6-四硫杂五环烯）的硒类似物1b-d已被合成。碘盐（1b）4I3表现出中等高度的导电性（σrt=13S cm−1），具有半导体温度依赖性，且给体排列为θ型。目前的θ型盐以及TMET-TTP盐位于θ相的普遍相图中的绝缘极限处。

  DOI：

  10.1246/cl.1998.253
• 作为产物：
  描述：

  4,5-双(2-氰乙基硫代)-1,3-二硫醇-2-硫酮 在 mercury(II) diacetate 、 亚磷酸三乙酯 作用下， 以 氯仿 、 溶剂黄146 为溶剂， 反应 17.67h， 生成 4,5-bis(cyanoethylthio)-1,3-dithiole-2-[(4,5-ethylenedithio)-1,3-dithiole-2-ylidene]
  参考文献：
  名称：

  The Chemistry of TTFTT; 1: New Efficient Synthesis and Reactions of Tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFTT): An Important Building Block in TTF-Syntheses

  摘要：

  报告了一种改进的、高效的四硫富戊烯-2,3,6,7-四硫醇酯 (TTFTT) 5 的合成方法。TTF-tetrathiolate 5 是在室温碱性条件下由 2,3,6,7-四(2′-氰乙基硫代)四硫代富勒烯 (11) 生成的，随后与一系列亲电体反应，以优异的收率合成了已知体系和新的 TTF 衍生物。

  DOI：

  10.1055/s-1994-25580

文献信息

• Preparation and Properties of Cyclopentadienyl- and Pentamethylcyclopentadienyl−Titanium(IV) Complexes with the C₈H₄S₈ Ligand, Electrical Conductivities of Their Oxidized Species, and X-ray Crystal Structure of Ti(C₅Me₅)₂(C₈H₄S₈)
  作者：Koyu Saito、Motohiro Nakano、Hatsue Tamura、Gen-etsu Matsubayashi

  DOI：10.1021/ic0000348

  日期：2000.10.1

  [Ti(C5Me5)(C8H4S8)2][TCNQ]0.3, with the C8H4S8 ligand-centered oxidation. They exhibited electrical conductivities of 1.6 x 10(-1) to 7.6 x 10(-4) S cm-1 measured for compacted pellets at room temperature. The crystal structure of 2 was clarified to consist of isolated dimerized units of the molecules through some sulfur-sulfur nonbonded contacts: monoclinic, P2(1)/c, a = 9.534(2) A, b = 18.227(2) A, c = 17.775(2) A

  Ti（C5H5）2（C8H4S8）（1），Ti（C5Me5）2（C8H4S8）（2），[NMe4] [Ti（C5H5）（C8H4S8）2]（3）和[NMe4] [Ti（C5Me5） （C8H4S8）2]（4）[C8H4S8（2-）= 2-（4,5-亚乙基二硫基）-1,3-二硫代-2-亚烷基）-1,3-二硫基-4,5-二硫代（2- ）]是通过将Ti（C5H5）2Cl2，Ti（C5Me5）2Cl2，Ti（C5H5）Cl3或Ti（C5Me5）Cl3与Li2C8H4S8或[NMe4] 2 [C8H4S8]在THF中反应制备的。它们被碘，二茂铁阳离子或TCNQ（7,7,8,8-四氰基-对-喹二甲烷）在CH2Cl2或丙酮中氧化，得到一电子氧化和一电子氧化的物种，[ Ti（C5H5）2（C8H4S8）.I3，[Ti（C5H5）2（C8H4S8）] [PF6]，[Ti（C5Me5）2（C8H4S8）]。I
• Structures of sulfur-rich dithiolate-gold(I) complexes and their oxidation
  作者：Tatsuya Ryowa、Motohiro Nakano、Hatsue Tamura、Gen-etsu Matsubayashi

  DOI：10.1016/j.ica.2004.03.048

  日期：2004.9

  [NMe 4 ][Au(PEt 3 )(C 3 S 5 )], [NMe 4 ][Au(PPh 3 )(C 3 S 5 )], [NMe 4 ][Au(PEt 3 )(C 8 H 4 S 8 )], [N-methylpyridinium][Au(PPh 3 )(C 8 H 4 S 8 )] [(PEt 3 )Au-C 3 S 5 -Au(PEt 3 )], and [(PEt 3 )Au-C 8 H 4 S 8 -Au(PEt 3 i)] [C 3 S 2 - 5 =4,5-disulfanyl-1,3-dithiole-2-thionate(2-); C 8 H 4 S 2 - 8 =2-(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2-)] were prepared. They exhibited

  [NMe 4] [Au（PEt 3）（C 3 S 5）]，[NMe 4] [Au（PPh 3）（C 3 S 5）]，[NMe 4] [Au（PEt 3）（C 8 H 4 S 8）]，[N-甲基吡啶] [Au（PPh 3）（C 8 H 4 S 8）] [（PEt 3）Au-C 3 S 5 -Au（PEt 3）]和[（PEt 3 ）Au-C 8 H 4 S 8 -Au（PEt 3 i）] [C 3 S 2-5 = 4,5-二硫烷基-1,3-二硫代-2-硫代酸酯（2-）; 制备C 8 H 4 S 2-8 ＝ 2-（4，5-亚乙基二硫代）-1，3-二硫代-2-亚基} -1，3-二硫代-4，5-二硫代（2-）]。由于在二氯甲烷中在-0.30至+0.21 V（vs. Ag / Ag +）处以二硫醇盐配体为中心的氧化作用，因此它们显示出了第一氧化电位。它们与碘或7,7,8,8-四氰基-对-喹二甲烷（T
• Synthesis of symmetrical and asymmetrical singly bridged bis-TTFs containing sulfur and selenium atoms. A study of some of their radical cation salts
  作者：Carole Carcel、Jean-Marc Fabre、Be´ne´dicte Garreau de Bonneval、Claude Coulon

  DOI：10.1039/b005790h

  日期：——

  By using a chalcogenolate (thiolate or selenolate) protection–deprotection strategy, a series of singly bridged bis-TTFs, 3a–c, 4a, have been prepared in high yield (84–96%) through two different routes. Route 2, involving the reaction between a monochalcogenolate TTF derivative with a previously prepared monoiodinated TTF species, appears to be a very useful and general strategy to selectively prepare

  通过使用硫族油酸酯（硫醇盐或硒醇盐）保护-脱保护策略，已通过两条不同的路线以高收率（84-96％）制备了一系列单桥双TTFs 3a – c，4a。路线2涉及单硫属元素化物TTF衍生物与先前制备的单碘化TTF物种之间的反应，这似乎是一种非常有用且通用的策略，可以选择性地高收率制备双TTF（84-90％）。双-的TTF， 图3a - Ç，4A，很容易转化成相应的二甲基化衍生物3A ' - ç '，4a中在基本（2当量）IMe介质中。该系列的双-TTF的给电子能力已经通过循环伏安法测定。供体3a，4a，3a' – c '的几种盐（主要是高氯酸盐）已通过电镀电合成获得为黑色粉末。已测量了它们在室温下作为压制粉末药丸的电导率，以及ESR信号的温度依赖性。
• Preparation and chemistry of new unsymmetrically substituted tetrachalcogenofulvalenes bearing CN(CH2)2X and HO(CH2)2X groups (X = S or Se)
  作者：Laurent Binet、Jean Marc Fabre、Claude Montginoul、Klaus Baek Simonsen、Jan Becher

  DOI：10.1039/p19960000783

  日期：——

  Several unsymmetrically substituted TTFs bearing the S(CH2)2CN protecting group have been prepared by standard cross coupling in triethyl phosphite from the key intermediate 4,5-bis(2′-cyanoethylsulfanyl)1,3-dithiol-2-one 1 and an appropriate 1,3-dichalcogenole-2-chalcogenone, 2–8. TTFs 10, 11 and 12 of type I have been obtained in satisfactory yields (30–60%) and those (13,14) of type II in low yields (10 and 19%) as a result of differences in the reactivity of the species involved.Pseudo-Wittig condensations from the key triphenylphosphonium salt 15 have allowed considerable improvement in the synthesis of 13 (70% yield) and 14 (57% yield).The diselena analogue of 1, 21 has also been obtained. Its derivative 22, a new tetrakis(alkylselena) functionalised TTF, has been isolated in fair yield (69%). Its deprotection in a basic medium followed by a subsequent alkylation has led to BEDSe-TTF 23 (40%). Finally, the same sequence of deprotectionrealkylation carried out from unsymmetric species 10 and 12 has successfully been used in a high yield preparation of the corresponding new functionalised TTFs bearing two hydroxyethyl groups.

  经过标准交叉耦合反应，从关键中间体4,5-双(2′-氰乙基硫基)-1,3-二噁烯-2-酮1和适当的1,3-二硫族化合物-2-硫族化合物2–8，制备了几种不对称取代的TTFs，这些TTFs含有S(CH2)2CN保护基。类型I的TTFs（10、11和12）产率令人满意（30-60%），而类型II的TTFs（13、14）因参与物种的反应性差异，产率较低（10%和19%）。从关键的三苯基膦盐15进行的伪维蒂希缩合反应，使得13（70%产率）和14（57%产率）的合成有了显著改善。同时，1的二硒类似物21也已被获得。其衍生物22，一种新的四烷基硒功能化的TTF，已以良好产率（69%）分离出来。其在碱性介质中的去保护反应，随后进行烷基化反应，得到了BEDSe-TTF 23（40%）。最后，从不对称物种10和12出发进行的相同去保护-再烷基化序列成功用于高产率制备相应的新功能化TTFs，且新TTFs中含有两个羟乙基作为取代基。
• Fabrication and Operation of Monolayer Mott FET at Room Temperature
  作者：Fan Yang、Masayuki Suda、Hiroshi M. Yamamoto

  DOI：10.1246/bcsj.20170233

  日期：2017.11.15

  Self-assembled monolayer FET based on a TTF derivative is described (FET = field-effect-transistor, TTF = tetrathiafulvalene). The molecule is anchored on an alumina dielectric layer through covalent bonding of a phosphonic acid linker. A p-type monolayer FET device is achieved and subsequent chemical doping of this monolayer with F4TCNQ dopants results in an ambipolar device. (F4TCNQ = 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane) Several strange behaviors including a gate voltage shift upon doping seem to be consistent with organic monolayer Mott FET. Finally, temperature dependence of the FET performance, which also fit the anticipated Mott FET behavior, is discussed.

  本文描述了一种基于TTF衍生物的自组装单分子层场效应晶体管（FET = 场效应晶体管，TTF = 四硫富瓦烯）。该分子通过磷酸酯连接子通过共价键固定在铝氧化物绝缘层上。实现了p型单分子层FET器件，随后对该单分子层进行F4TCNQ掺杂，结果形成了双极器件。（F4TCNQ = 2,3,5,6-四氟-7,7,8,8-四氰基喹啉二甲烷）包括掺杂后栅电压偏移在内的几种奇特行为似乎与有机单层Mott FET一致。最后，讨论了FET性能的温度依赖性，这也符合预期的Mott FET行为。