2-formylmethylidene-4,5-bis(methoxycarbonyl)-1,3-dithiole | 88312-73-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-formylmethylidene-4,5-bis(methoxycarbonyl)-1,3-dithiole
• 英文别名: Dimethyl 2-(2-oxoethylidene)-1,3-dithiole-4,5-dicarboxylate
• CAS: 88312-73-6
• 化学式: C₉H₈O₅S₂
• 分子量: 260.292
• InChiKey: YUNBHDKMSIZOBG-UHFFFAOYSA-N

物化性质

• 熔点：
  111-115 °C
• 沸点：
  361.2±42.0 °C(Predicted)
• 密度：
  1.561±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-formylmethylidene-4,5-bis(methoxycarbonyl)-1,3-dithiole 在 lithium diisopropyl amide 、 三甲氧基磷 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.33h， 生成 2-[4,5-bis(methoxycarbonyl)-1,3-diselenol-2-ylidene]-5-{2-[4,5-bis(methoxycarbonyl)-1,3-diselenol-2-ylidene]ethylidene}-1,3,4,6-tetrathiapentalene
  参考文献：
  名称：

  Preparation, structures and physical properties of selenium analogues of DTEDT as promising donors for organic metals

  摘要：

  我们合成了 DTEDT [2-(1,3-二硫醇-2-亚基)-5-[2-(1,3-二硫醇-2-亚基)亚乙基]-1,3,4,6-四硫杂戊烯] 的三种硒类似物。它们显示了四对单电子氧化还原波。E1 值比 DTEDT 略高 0.02-0.05 V。另一方面，E2-E1 值几乎与 DTEDT 相等。它们的 TCNQ 复合物和阳离子自由基盐显示出相当高的导电性，而且有几种盐显示出金属导电性。特别是 DTEDS 的 ReO4- 盐和 Au(CN)2- 盐以及 DSEDS 的 SbF6- 盐、TaF6- 盐和 I3- 盐在 1.5-4.2 K 温度下表现出稳定的金属特性。对金属盐 (DSEDS)3TaF6 的 X 射线晶体结构分析表明，这种盐具有与超导 (DTEDT)3Au(CN)2 相似的供体分子二维 β 型堆积结构。计算得出的 (DSEDS)3TaF6 费米面是一个二维封闭椭圆体。

  DOI：

  10.1039/b002790l
• 作为产物：
  描述：

  [4,5-bis-(Methoxycarbonyl)-1,3-dithiol-2-yl]tributyl-phosphonium tetrafluoroborate 、 草酸醛 以70%的产率得到
  参考文献：
  名称：

  YOSHIDA, ZEN-ICHI;KAWASE, TOKUZO;AWAJI, HIROSHI;SUGIMOTO, IWAO;SUGIMOTO, +, TETRAHEDRON LETT., 1983, 24, N 33, 3469-3472

  摘要：

  DOI：

文献信息

• Nitroso derivatives of 1,3-dithiol-2-ylidene stabilised by intramolecular oxygen ? sulfur interactions: synthesis and X-ray crystal structures.
  作者：Martin R. Bryce、Michael A. Chalton、Andrei S. Batsanov、Christian W. Lehmann、Judith A. K. Howard

  DOI：10.1039/p29960002367

  日期：——

  A series of 2-(nitrosomethylene)-1,3-dithiole derivatives 3 have been synthesised, and X-ray crystal structures of compounds 3g, 3h and 3I have been obtained. The coplanarity of the dithiole ring and the nitroso group in all three compounds favours π-conjugation, and short intramolecular oxygen ⋯ sulfur contacts (ca. 2.4 Å) occur between the nitrosyl oxygen and a sulfur atom of the dithiole ring; these structural features explain the stability and unreactivity of the series of compounds 3.

  一系列2-(亚硝基亚甲基)-1,3-二硫环烯衍生物3已被合成，并获得了化合物3g、3h和3i的X射线晶体结构。这三种化合物中二硫环与亚硝基团的平面共平性有利于π-共轭，且亚硝氧与二硫环中的一个硫原子之间发生短的分子内氧-硫接触（约2.4 Å）；这些结构特征解释了系列化合物3的稳定性和不反应性。
• Fluorene acceptors with intramolecular charge-transfer from 1,3-dithiole donor moieties: novel electron transport materials
  作者：Igor F. Perepichka、Dmitrii F. Perepichka、Anatolii F. Popov、Igor F. Perepichka、Martin R. Bryce、Leonid M. Goldenberg、Antony Chesney、Adrian J. Moore、Judith A. K. Howard、Lyudmila G. Kuz’mina、Nikolai I. Sokolov

  DOI：10.1039/a800912k

  日期：——

  The synthesis, solution redox behaviour and intramolecular charge transfer properties of novel D(CH–CH)nA compounds (n = 0, 1, 3; D and A are 1,3-dithiole and nitrofluorene moieties, respectively) are reported.

  报道了新型D(CH–CH)nA化合物（n = 0, 1, 3；D和A分别为1,3-二噻烷和硝基芴基部分）的合成、溶液氧化还原行为及分子内电荷转移特性。
• 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 new 2-mono and 2,3-bis(hydroxymethyl)-6,7-ethylenedithio TTF vinylogs
  作者：Catherine Guillot、Piétrick Hudhomme、Philippe Blanchard、Alain Gorgues、Michel Jubault、Guy Duguay

  DOI：10.1016/0040-4039(95)00085-q

  日期：1995.3

  The synthesis of title compounds prone to generate hydrogen bonds thanks to their alcohol functionalities is depicted. Cyclic voltammetry proves these derivatives to be strong π-donors, able to act as convenient precursors of related organic metals.

  描述了由于其醇官能度而易于产生氢键的标题化合物的合成。循环伏安法证明了这些衍生物是强大的π供体，能够用作相关有机金属的便捷前体。
• 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
  作者：Adrian J. Moore、Martin R. Bryce、Andrei S. Batsanov、Andrew Green、Judith A. K. Howard、Anthony Mckervey、Peter Mcguigan、Isabelle Ledoux、Enrique Ortí、Rafael Viruela、Pedro M. Viruela、Brian Tarbit

  DOI：10.1039/a708078f

  日期：——

  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.