4,5-ethylenedioxy-1,3-dithiole-2-thione | 128457-00-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,5-ethylenedioxy-1,3-dithiole-2-thione
• 英文别名: 2,5-dioxa-7,9-dithiabicyclo<4.3.0>non-1(6)-en-8-thione；2H,3H-1,3-Dithioleno[4,5-e]1,4-dioxin-6-thione；4,5-(ethylenedioxy)-1,3-dithiol-2-thione；4,5-ethylenedioxy-1,3-dithiol-2-thion；1,3-Dithiolo[4,5-b][1,4]dioxin-2-thione, 5,6-dihydro-；5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxine-2-thione
• CAS: 128457-00-1
• 化学式: C₅H₄O₂S₃
• mdl: MFCD01096283
• 分子量: 192.284
• InChiKey: BPUFOIWSJHRPCW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 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：
  101
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,5-ethylenedioxy-1,3-dithiole-2-thione 在 lithium bromide 、 亚磷酸三乙酯 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 5.75h， 生成 4,5-ethylenedioxy-tetrathiafulvalene
  参考文献：
  名称：

  Syntheses, Structure and Conducting Properties of Halogenated Ethylenedioxytetrathiafulvalenes

  摘要：

  4,5-Diiodo-, 4,5-dibromo-, and 4,5-dichloro-4',5'-ethylenedioxytetra-thiafulvalenes (EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2) were synthesized in moderate to good yields by the two routes. The first route contains the reaction of EDO-TTF with LDA, followed by quenching with halogenated reagents, and the second route consists of the P(OR)(3)-mediated cross-coupling of 4,5-dihalogenated 1,3-dithiole-2-ones with 4,5-ethylenedioxy-1,3-dithiole-2-thione. The structures of EDO-TTFI2 and EDO-TTFCl2 were determined by X-Ray analysis. The radical-cation salts derived from EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2 show high conductivities, although these compounds contain electron-withdrawing halogens as the substituent.

  DOI：

  10.3987/com-00-s(i)79
• 作为产物：
  描述：

  trans-(1,4-dioxan-2,3-diyl)-bis(N-morpholinodithiocarbamate) 在 硫化氢 、 溴 作用下， 以 二氯甲烷 、 氯仿 、 水 为溶剂， -30.0~200.0 ℃ 、26.66 Pa 条件下， 反应 0.33h， 生成 4,5-ethylenedioxy-1,3-dithiole-2-thione
  参考文献：
  名称：

  1,4-Dioxane-2,3-dithione, the First Cyclic Dithioxooxalate

  摘要：

  1,4-二恶烷-2,3-二硫酮（13）已经通过前体10的光化学脱羰反应制备得到。化合物13在室温下不稳定，并在形成（4 + 2）环加成物15-19的过程中被截获。

  DOI：

  10.1055/s-1990-26853

文献信息

• 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。
• Unsymmetrically Substituted Ethylenedioxytetrathiafulvalenes
  作者：Takehiko Mori、Hiroo Inokuchi、Aravinda M. Kini、Jack M. Williams

  DOI：10.1246/cl.1990.1279

  日期：1990.8

  Seven new electron donors, 4,5-ethylenedioxytetrathiafulvalenes where 4′,5′-substituents are trimethylenedithio, ethylenedithio, methylenedithio, 2-oxatrimethylenedithio, methylthio, hydrogen and methyl carboxylate, are prepared, and their electrochemical properties are investigated.

  制备了七种新的电子供体--4,5-亚乙二氧基四硫杂戊烯，其中 4′,5′-取代基为三亚甲基二硫、亚乙基二硫、亚甲基二硫、2-氧杂三亚甲基二硫、甲硫基、氢和羧酸甲酯。
• Ethylenedithio(ethylenedioxo)diselenadithiafulvalene (TOST) and ethylenediseleno(ethylenedioxo)tetrathiafulvalene (SO): new unsymmetrical π-donors containing three elements in Group 16 (O, S, and Se)
  作者：Tatsuro Imakubo、Yoshinori Okano、Hiroshi Sawa、Reizo Kato

  DOI：10.1039/c39950002493

  日期：——

  The synthesis and characterization of new unsymmetrical bis(ethylenedithio)tetrathiafulvalene (ET) analogues ethylenedithio(ethylenedioxo)diselenadithiafulvalene (TOST) and ethyl enediseleno(ethylenedioxo)tetrathiafulvalene (SO) that contain three elements in group 16(O, S and Se) and their cation radical salts are reported.

  新型不对称双（亚乙基二硫代）四硫富瓦烯（ET）类似物的合成和表征，亚乙基二硫（亚乙基二氧代）二亚硒二硫富瓦烯（TOST）和乙基烯二烯丙基（亚乙基二氧代）四硫富富瓦烯（SO），它们在第16组（O，S和Se）中包含三个元素报道了阳离子自由基盐。