(4,5-Bis-methylsulfanyl-[1,3]dithiol-2-ylidene)-acetaldehyde | 140934-19-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯基硫酯
• 英文名称: (4,5-Bis-methylsulfanyl-[1,3]dithiol-2-ylidene)-acetaldehyde
• 英文别名: 2-[4,5-Bis(methylsulfanyl)-1,3-dithiol-2-ylidene]acetaldehyde
• CAS: 140934-19-6
• 化学式: C₇H₈OS₄
• 分子量: 236.404
• InChiKey: PUBMMGFESDSFAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  118
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  二(三甲基硅基)碳酰二亚胺 、 (4,5-Bis-methylsulfanyl-[1,3]dithiol-2-ylidene)-acetaldehyde 在 吡啶 、 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以85%的产率得到
  参考文献：
  名称：

  New 1,3-dithiol-2-ylidene donor–π–acceptor chromophores with intramolecular charge-transfer properties, and related donor–π–donor molecules: synthesis, electrochemistry, X-ray crystal structures, non-linear optical properties and theoretical calculations

  摘要：

  New donor-pi-acceptor chromophores 5a-c, 7a-c, 8a-c, 13a-c and 14b-c have been synthesised: substituted 1,3-dithiole derivatives span a range of donor abilities [viz. 4,5-dimethyl > 4,5-bis(methylsulfanyl) > 4,5-bis(methoxycarbonyl)], a conjugated ethylenic or oligoethylenic linker varies the central pi-electron unit tone, two and four conjugated double bonds) and dicyanomethylene and N-cyanoimine groups are the acceptor units. Extended tetrathiafulvalene derivatives 15a-c have also been synthesised. The electronic absorption spectra of compounds 5, 7, 8 and 14 reveal a broad low-energy intramolecular charge-transfer band [lambda(max)(MeCN) 354-533 nm] which shifts bathochromically with increasing donor strength of the dithiole ring, and with increasing length of the conjugative pathway. The solution redox properties of 5, 7, 8 and 14, studied by cyclic voltammetry, reveal a reversible one-electron oxidation wave, attributed to the formation of the radical cation of the 1,3-dithiol-2-ylidene moiety, and an irreversible one-electron reduction to form the radical anion located on the dicyanomethylene or N-cyanoimine groups. For the bis(dithiole) donors 15a-c a single two-electron redox wave is observed. The non-linear optical (NLO) properties of 7a-c and 14b have been determined using the EFISH technique: moderate NLO properties are observed for compounds 7a-c [mu.beta(0) 85-112 x 10(-48) esu] whereas for the more extensively conjugated compound 14b, the value is increased to mu.beta(0) 1170 x 10(-48) esu. The molecular structure and electronic properties of the unsubstituted (R = H) compounds 7, 8, 1 8 and 15 have been calculated within the density functional theory approach. The minimum energy conformation corresponds to the trans orientation of the side chain for 7, and the cis orientation for 8, in agreement with X-ray crystal structures and solution NMR data. The redox properties and electronic spectra are discussed on the basis of molecular orbital energies and topologies. The X-ray crystal structures of compounds 7b, 8b and 15b are reported. In 7b the 1,3-dithiol-2-ylidene and dicyanopropene systems are planar and form an angle of 3 degrees between each other; the 'butadiene' unit has a trans configuration. Molecule 8b is planar (with the exception of the methyl groups) and the imine nitrogen atom is in a syn orientation towards the dithiole group, forming a short intramolecular S ... N contact [2.719(6) Angstrom]. For both 7b and 8b pi-delocalisation is observed within the central conjugated spacer unit. Molecule 15b has a predominantly planar structure, with the central tetraene unit in an all-trans configuration.

  DOI：

  10.1039/a708078f
• 作为产物：
  描述：

  草酸醛 、 4,5-bis(methylthio)-1,3-dithiolium tetrafluoroborate 生成 (4,5-Bis-methylsulfanyl-[1,3]dithiol-2-ylidene)-acetaldehyde
  参考文献：
  名称：

  New vinylogous tetrathiafulvalene (TTF) π-electron donors

  摘要：

  The synthesis and solution electrochemistry of ten new ethanediylidene-2,2'-bis(1,3-dithiole) derivatives (7)-(16) is described; charge-transfer complexes have been obtained with tetracyano-p-quinodimethane (TCNQ).

  DOI：

  10.1016/s0040-4039(00)91626-5

文献信息

• Synthesis and Properties of New Tetrathiapentalene Donors Composed of Vinylogous TTFs
  作者：Shintaro Iwamoto、Shunsuke Watanabe、Hiroyuki Fueno、Kazuyoshi Tanaka、Yohji Misaki

  DOI：10.1246/cl.2008.82

  日期：2008.1.5

  A bis-fused donor composed of TTF vinylogues, 2,5-bis (2 -ethanediylidene -1,3-dithiole)-1,3,4,6-tetrathiapentalene (BisEDT, la) and its derivatives have been synthesized. Cyclic voltammograms of 1 consist of four-pairs of one-electron redox waves. X-ray structure analysis of tetrakis(methylthio)-1 (1b) reveals the donor adopts almost planar structure. The TCNQF 4 complexes of 1 showed moderate conductivity

  已经合成了由 TTF 乙烯基化合物、2,5-双（2-乙二亚基-1,3-二硫醇）-1,3,4,6-四硫戊烯（BisEDT，la）及其衍生物组成的双稠合供体。1 的循环伏安图由四对单电子氧化还原波组成。四（甲硫基）-1 (1b) 的 X 射线结构分析显示供体采用几乎平面结构。1 的 TCNQF 4 复合物在压缩颗粒上显示出 σ rt = 10 -2 S cm -1 的中等电导率。
• New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries
  作者：Shintaro Iwamoto、Yuu Inatomi、Daisuke Ogi、Satoshi Shibayama、Yukiko Murakami、Minami Kato、Kazuyuki Takahashi、Kazuyoshi Tanaka、Nobuhiko Hojo、Yohji Misaki

  DOI：10.3762/bjoc.11.128

  日期：——

  Derivatives of tris-fused TTF extended with two ethanediylidenes (5), tris- and pentakis-fused TTFs extended with two thiophene-2,5-diylidenes (6–9) were successfully synthesized. Cyclic voltammograms of the tetrakis(n-hexylthio) derivative of 5 and 7 (5d, 7d) consisted of two pairs of two-electron redox waves and two pairs of one-electron redox waves. On the other hand, four pairs of two-electron redox waves and two pairs of one-electron redox waves were observed for the tetrakis(n-hexylthio) derivative of 9 (9d). Coin-type cells using the bis(ethylenedithio) derivatives of 5 (5b), 6 (6b) and the tetrakis(methylthio) derivatives of 5 (5c) and 8 (8c) as positive electrode materials showed initial discharge capacities of 157–190 mAh g⁻¹ and initial energy densities of 535–680 mAh g⁻¹. The discharge capacities after 40 cycles were 64–86% of the initial discharge capacities.

  三联噻吩并三噻吩并二乙烯基扩展衍生物 (5)、三联噻吩并五噻吩并二噻吩-2,5-二基扩展衍生物 (6-9) 成功合成。四乙硫代己烷基衍生物的 5 和 7 (5d，7d) 的循环伏安图包含两对双电子氧化还原波和两对单电子氧化还原波。另一方面，四对双电子氧化还原波和两对单电子氧化还原波被观察到在四乙硫代己烷基衍生物的 9 (9d) 中。使用 5 (5b) 和 6 (6b) 的二乙烯基硫代衍生物以及 5 (5c) 和 8 (8c) 的四甲硫代衍生物作为正极材料的硬币型电池显示出初始放电容量为157-190mAh/g和初始能量密度为535-680mAh/g。40个循环后的放电容量为初始放电容量的64-86%。
• Syntheses, structure and properties of vinylogous EDO-TTFs
  作者：T. Shirahata、T. Morikawa、H. Miyamoto、Y. Nakano、H. Yamochi、Y. Misaki

  DOI：10.1016/j.physb.2009.12.024

  日期：2010.6

  the dication state. X-ray crystal structure analysis of BMCEDO-EBDT reveals that the inter-molecular C-H···O type hydrogen bond is constructed between the hydrogen atom and the oxygen atom of the ethylenedioxy group. Single crystalline TCNQ complexes of DMEDO-EBDT and BTMEDO-EBDT have been prepared and their conducting properties and crystal structure have been investigated. The TCNQ complexes of DMEDO-EBDT

  我们合成了插烯 4,5-ethylenedioxy-tetrathiafulvalenes (EDO-TTFs), 4,5-ethylenedioxy-2,2'-ethanediylidenebis(1,3-dithiole) (EDO-EBDT), 4,5-dimethyl-4', 5'-ethylenedioxy-2,2'-ethanediylidene-bis(1,3-dithiole) (DMEDO-EBDT), 4,5-bis(thiomethyl)-4',5'-ethylenedioxy-2,2'-ethanediylidenebis ( 1,3-dithiole) (BTMEDO-EBDT) 和 4,5-bis(methoxycarbonyl)-4',5'-ethylenedioxy-2,2'-ethanediylide-nebis(1,3-dithiole) (BMCEDO-EBDT)
• Synthesis and Properties of Novel [5]Radialenes Substituted with Multiple 1,3-Dithiol-2-yildenes
  作者：Masafumi Ueda、Yui Ogura、Yohji Misaki

  DOI：10.1246/cl.130140

  日期：2013.5.5

  Novel [5]radialenes with four 1,3-dithiol-2-ylidene (DT) units (2) and ethylene analogs of [5]dendralene derivatives with five DT units (3) were synthesized. Cyclic voltammetry revealed that 2 exhi...

  合成了具有四个 1,3-二硫醇-2-亚基 (DT) 单元 (2) 的新型 [5] radialene 和具有五个 DT 单元 (3) 的 [5] 枝烯衍生物的乙烯类似物。循环伏安法显示，2...
• New extended analogues of TTF via triethylphosphite-mediated reaction
  作者：Philippe Leriche、Sophie Roquet、Nicolas Pillerel、Gilles Mabon、Pierre Frère

  DOI：10.1016/s0040-4039(03)00024-8

  日期：2003.2

  New extended derivatives of TTF bearing cyanoethylsulfanyl or furan groups which cannot be obtained by Wittig-type reaction with Akiba's reagent have been synthesized using a clean, cheap-step and rapid methodology; their electrochemical and optical behavior are studied. (C) 2003 Elsevier Science Ltd. All rights reserved.