5,6-dihydro-[1,4]diselenino[2,3-d][1,3]dithiole-2-thione | 118355-60-5

• 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: 5,6-dihydro-[1,4]diselenino[2,3-d][1,3]dithiole-2-thione
• 英文别名: 4,5-(ethylenediseleno)-1,3-dithiole-2-thione；4,5-ethylenediseleno-1,3-dithiole-2-thione
• CAS: 118355-60-5
• 化学式: C₅H₄S₃Se₂
• 分子量: 318.205
• InChiKey: RCUUIJRVOSPOTH-UHFFFAOYSA-N

物化性质

• 沸点：
  368.4±52.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.05
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  82.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,6-dihydro-[1,4]diselenino[2,3-d][1,3]dithiole-2-thione 在 mercury(II) diacetate 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 生成 4,5-ethylenediseleno-1,3-dithiol-2-one
  参考文献：
  名称：

  Papavassiliou, G. C.; Kakoussis, V. C.; Lagouvardos, D. J., Molecular Crystals and Liquid Crystals (1969-1991), 1990, vol. 181, p. 171 - 184

  摘要：

  DOI：
• 作为产物：
  描述：

  三硫代碳酸亚乙烯酯 、 1,2-bis(selenocyanato)ethane 在 lithium diisopropyl amide 作用下， 生成 5,6-dihydro-[1,4]diselenino[2,3-d][1,3]dithiole-2-thione
  参考文献：
  名称：

  Neue selenreiche 1,3-Dichalkogenol-2-selone via 4,5-Dilithio-1,3-dichalkogenol-2-selone

  摘要：

  1,3-Dithiole-2-thione (1), 1,3-diselenole-2-selone (2), 1,3-thiaselenole-2-thione (3), 1,3-dithiole-2-selone (4), 1,3-diselenole-2-thione (5) and 1,3-thiaselenole-2-selone (6) are dilithiated with lithium diisopropyl amide in the 4/5 position, followed by selenation (thiolation) and complexation of the resulting heterocyclic diselenolates (dithiolates) to the zinc bis-chelates (tetrabutylammonium or tetraphenylphosphonium salts).These zinc complexes react with benzoyl chloride to the corresponding selenole and thiole esters. It is noteworthy that the heterocyclic thiones with one or two ring selenium atoms undergo ring transformation (Dimroth rearrangement) during the lithiation chalcogenation sequence, whilst the thione sulfur and one ring selenium atom change their places: 3 --> 1,3-dithiole-2-selone-4,5-diselenolate or dithiolate structure, 5 --> 1,3-thiaselenole-2-selone-4,5-diselenolate structure. This observed rearrangement is verified by independent synthetic pathways. The corresponding identical zinc chelates 12 and complex 18 result from the precursors 3 and 4, and 5 and 6, respectively. Trapping experiments support the conclusion that this rearrangement takes place already during lithiation. The zinc chelates and thiole and selenole esters are characterized in detail by IR and above all by C-13 and Se-77 NMR spectroscopy, including NMR shift values of the precursor heterocycles. The X-ray crystal structure determination of bis(tetraphenylphosphonium)-bis(1,3-thiaselenole-2-selone-4,5-diselenolato) zincate (18), obtained from 5, shows the rearrangement of 5 to the 1,3-thiaselenole-2-selone partial structure in 18.

  DOI：

  10.1016/0022-328x(92)83086-w

文献信息

• Conducting Salts Composed of Selenium Analogues of TMET-TTP
  作者：Takehiko Mori、Minoru Ashizawa、Masanobu Aragaki、Kyoji Murata、Yohji Misaki、Kazuyoshi Tanaka

  DOI：10.1246/cl.1998.253

  日期：1998.3

  Selenium analogues of TMET-TTP (2-(4,5-bisthiomethyl-1,3-dithiol-2-ylidene)-5-(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene) 1b-d have been synthesized. The iodine salt (1b)4I3 exhibits moderately high conductivity (σrt=13S cm−1) with semiconducting temperature dependence, and the donor arrangement is θ-type. The present θ-type salt as well as TMET-TTP salts is located at the insulating limit in the universal phase diagram of θ-phases.

  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。
• 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。
• Synthesis of Selenated Unsymmetrical Analogs of BEDT-TTF, BEDO-TTF and DMET
  作者：Laurent Binet、Jean Marc Fabre、Jan Becher

  DOI：10.1055/s-1997-1494

  日期：1997.1

  An improved synthesis of EDSEDT-TTF 4 and EDSEDO-TTF 5 from appropriate cross-coupling reactions involving 4,5-bis(2-cyanoethylthio)-1,3-dithiol-2-one (9) and 4,5-bis(2-cyanoethylseleno)-1,3-dithiol-2-one (11) as key intermediates is described. Moreover, a Wittig-type preparation of new selenated derivatives 6 and 7 of DMET molecule from the useful new precursor [4,5-bis(2-cyaoethylseleno)-1,3-dithiol-2-yl]triphenylphosphonium tetrafluoroborate (17) is presented.

  描述了一种改进的合成方法，通过合适的交叉偶联反应，利用4,5-二(2-氰乙基硫)-1,3-二硫醇-2-酮（9）和4,5-二(2-氰乙基硒)-1,3-二硫醇-2-酮（11）作为关键中间体，合成EDSEDT-TTF 4和EDSEDO-TTF 5。此外，还展示了一种Wittig型合成方法，利用有用的新前体[4,5-二(2-氰乙基硒)-1,3-二硫醇-2-基]三苯基磷四氟硼酸盐（17），制备DMET分子的新的硒化衍生物6和7。
• 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 and properties of hetero-halogenated TTFsElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/ob/b3/b310822h/
  作者：Rie Suizu、Tatsuro Imakubo

  DOI：10.1039/b310822h

  日期：——

  Novel hetero-halogenated TTFs containing both chlorine and iodine atoms were prepared and their unique characters based on the halogen atoms were examined.

  制备了新型含有氯和碘原子的异卤化TTFs，并对其基于卤素原子的独特特性进行了研究。