2,3-bis(2-cyanoethylthio)-6,7-dimethyltetrathiafulvalene | 177659-02-8

• 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: 2,3-bis(2-cyanoethylthio)-6,7-dimethyltetrathiafulvalene
• 英文别名: 3,3'-((4',5'-dimethyl-[2,2'-bi(1,3-dithiolylidene)]-4,5-diyl)bis(sulfanediyl))dipropanenitrile；4,5-bis(2'-cyanoethylthio)-4,5-dimethyl-tetrathiafulvalene；3-[[5-(2-Cyanoethylsulfanyl)-2-(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 177659-02-8
• 化学式: C₁₄H₁₄N₂S₆
• 分子量: 402.675
• InChiKey: JSDPRHSKYIKUEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  199
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,3-bis(2-cyanoethylthio)-6,7-dimethyltetrathiafulvalene 在 cesium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.75h， 生成 2-{4-[3-(4',5'-Dimethyl-5-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanyl)-propylsulfanyl]-5-methylsulfanyl-[1,3]dithiol-2-ylidene}-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine
  参考文献：
  名称：

  含硫和硒原子的对称和不对称单桥双TTF的合成。对某些自由基阳离子盐的研究

  摘要：

  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。

  DOI：

  10.1039/b005790h
• 作为产物：
  描述：

  4,5-双(2-氰乙基硫代)-1,3-二硫醇-2-硫酮 在 乙酸酐 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 2,3-bis(2-cyanoethylthio)-6,7-dimethyltetrathiafulvalene
  参考文献：
  名称：

  基于四甲基-TTP的有机分子导体：由阴离子尺寸和形状调节的结构和电学性质

  摘要：

  成功合成了双稠合四硫富瓦烯的四甲基衍生物 2,5-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (TMTTP)。大多数由 TMTTP 组成的自由基阳离子盐在单晶上具有 σ rt = 10 1至 10 2 S cm –1的高电导率。TMTTP 导体的阴离子形状和尺寸调节电性能。PF 6 –和 AsF 6 –盐表现出低至 10 K 的金属电导率，而 ReO 4 –和 AuI 2 –盐分别在 126 和 11 K 时显示出金属到绝缘体 (MI) 的转变。(TMTTP) 2 X (X = PF 6 , AsF 6 , BF 4 , 和 ReO 4 ) 和 (TMTTP) 3 AuI 2的单晶 X 射线结构分析表明，供体堆积基序被归类为所谓的β型。(TMTTP) 2 X (X = ReO 4、BF 4、PF 6和AsF

  DOI：

  10.1021/acs.inorgchem.1c04004

文献信息

• 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。
• Synthesis, redox behaviour and X-ray structure of bis-TTF containing a pyridine unit as a potential building block in the construction of conducting magnetic materials
  作者：Sabrina Bouguessa、Katel Hervé、Stéphane Golhen、Lahcène Ouahab、Jean-Marc Fabre

  DOI：10.1039/b208624g

  日期：2003.2.27

  The synthesis of singly and doubly bridged bis-TTF containing a 2,6-bis(methylthio)pyridine group as a linker and potentially usable as a ligand for paramagnetic transition metal complexes is reported. Cyclisation leading to doubly bridged bis-TTF has been achieved without using the high dilution technique generally employed in such cases. The redox behaviour of such precursors has been studied by

  含2,6-双（甲硫基）吡啶基团作为连接基的单双桥双-TTF的合成，可能用作 配体 用于顺磁性过渡金属配合物的报道。 环化无需使用在这种情况下通常使用的高稀释技术就可以实现双桥双TTF的合成。此类前体的氧化还原行为已通过循环伏安法和方波技术。其中之一的晶体结构电子给体 由...决定 X射线衍射 示出了TTF单元的堆叠布置。
• Synthesis and study of radical cation salts and TCNQ charge transfer complexes of a series of tetrathiafulvalenes (TTF) substituted by one or two hydroxylated side chain(s): –SCH2CH2OH
  作者：Jean-Pierre Legros、Françoise Dahan、Laurent Binet、Carole Carcel、Jean-Marc Fabre

  DOI：10.1039/b003009k

  日期：——

  Unsymmetrically substituted tetrathiafulvalene derivatives containing hydroxy group(s) on side-chain(s) have been synthesized from cyano precursors via either a cross-coupling reaction or a Wittig-type condensation. As deduced from cyclic voltammetry data, the electron donor properties of the obtained compounds have been found to be similar to those of BEDTTTF. A series of radical cation salts derived from these donors has been obtained by electrocrystallization and charge transfer complexes have been prepared chemically by using TCNQ as an electron acceptor. The electrical conductivity of these phases ranges from 3 × 10−2 to 7 × 10−7 S cm−1 which is consistent with their structural features. X-Ray structural analysis of three of the radical cation salts with monovalent closed-shell anions (Br−, ClO4−) indicates a 1 ∶ 1 stoichiometry which implies that, in each case, the donor has been oxidized to the D+ state. In the same way, a crystal structure made of stacks where the donor and the acceptor molecules alternate has been found for a charge transfer complex between TCNQ and a donor derived from EDTTTF. The crystal structure of one of the donors indicates that the flexibility of the hydroxylated side chains appears as a favourable feature for the formation of hydrogen bonds.

  侧链上含有羟基的不对称取代的四硫富瓦烯衍生物已由氰基前体通过交叉偶联反应或维蒂希型缩合合成。根据循环伏安法数据推断，所得化合物的电子供体性质与 BEDTTTF 相似。通过电结晶获得了一系列由这些供体衍生的自由基阳离子盐，并使用 TCNQ 作为电子受体化学制备了电荷转移络合物。这些相的电导率范围为3×10×2至7×10×7S cm×1，这与其结构特征一致。三种自由基阳离子盐与一价闭壳阴离子（Br-、ClO4-）的 X 射线结构分析表明，化学计量为 1 - 1，这意味着在每种情况下，供体已被氧化为D+状态。以同样的方式，对于 TCNQ 和源自 EDTTTF 的供体之间的电荷转移络合物，发现了由供体和受体分子交替的堆叠组成的晶体结构。其中一个供体的晶体结构表明，羟基化侧链的柔性似乎是形成氢键的有利特征。
• Single-component Magnetic Molecular Conductor [Fe(dmdt)₂] (dmdt: dimethyltetrathiafulvalenedithiolate)
  作者：Biao Zhou、Satomi Ogura、Noriko Kato、Yuki Idobata、Akiko Kobayashi、Hayao Kobayashi

  DOI：10.1246/cl.130323

  日期：2013.9.5

  Molecular metal complexes with interactions between localized spins and conduction electrons are expected to show interesting electronic and magnetic properties. We prepared magnetic molecular cond...

  具有局域自旋和传导电子之间相互作用的分子金属配合物有望显示出有趣的电子和磁特性。我们制备了磁性分子...
• Synthesis of New Functionalized π-Electron Donors: Primary Hydroxy and Primary Amino Multisulfur Tetrathiafulvalenes
  作者：Laurent Binet、Jean-Marc Fabre

  DOI：10.1055/s-1997-1321

  日期：1997.10

  The synthesis of new primary hydroxy- and aminotetrathiafulvalenes is described. The hydroxy derivatives 3a and 3b were synthesized from protected TTF thiolates while the amino derivatives 14a, 14b and 17 were prepared from the corresponding hydroxyTTFs using Gabriel synthesis or azide reduction. The synthesis of new amphiphilic bis(hydroxy)- and bis(amino)TTFs is also reported.

  本文描述了新的主羟基和氨基四硫富瓦烯的合成。羟基衍生物3a和3b由受保护的TTF硫醇合成，而氨基衍生物14a、14b和17则由相应的羟基TTF通过加布里埃尔合成或叠氮化物还原制备。本文还报道了新的双亲性双（羟基）和双（氨基）TTF的合成。