Methyl 2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-dithiole-4-carboxylate | 135418-75-6

• 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: Methyl 2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-dithiole-4-carboxylate
• CAS: 135418-75-6
• 化学式: C₁₀H₈O₂S₆
• 分子量: 352.568
• InChiKey: LIZKFDIEHXNECT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  178
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Methyl 2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-dithiole-4-carboxylate 在 吡啶 、 lithium hydroxide 、 草酰氯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 为溶剂， 反应 19.0h， 生成 4,5-ethylenedithio-4'-(N,N-dimethylcarbamoyl)tetrathiafulvalene
  参考文献：
  名称：

  The crystal chemistry of amide‐functionalized ethylenedithiotetrathiafulvalenes: EDT‐TTF‐CONRR′ (R, R′ = H, Me)

  摘要：

  本文描述了在TTF核心上直接官能化的乙烯基二硫代四硫富瓦烯（EDT-TTF）的制备，该官能团具有伯、仲或叔酰胺或酰肼官能团。本文报道了EDT-TTF-CO2H、EDT-TTF-CONH2、EDT-TTF-CONHMe和EDT-TTF-CONMe2的X射线晶体结构。这些官能化分子采用的固态结构似乎是氢键要求之间的折衷，氢键分别由OH、NH2、CH和CO基团提供和接受，而EDT-TTF部分的S·S·S范德华相互作用。TTF核心氢原子的活化，邻位于酰胺基，增强了其参与短C-H·O键的能力，从而产生在仲酰胺EDT-TTF-CONHMe中观察到的特征螯合R2R1(7)结构。

  DOI：

  10.1039/a902852h
• 作为产物：
  描述：

  4,5-二亚乙基二硫代-1,3-二硫醇-2-硫酮 、 2-oxo-1,3-dithiol-4-carboxylic acid methyl ester 在 三甲氧基磷 作用下， 以13%的产率得到Methyl 2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-dithiole-4-carboxylate
  参考文献：
  名称：

  2-Mono or 2,3-Bis(hydroxymethyl)-6,7-ethylenedithio-tetrathiafulvalenes: New potential precursors of organic metals endowed with hydrogen bonds

  摘要：

  The syntheses of new pi-unsymmetrical donors of the TTF family having half moiety of bis(ethylenedithio)-TTF (BEDT-TTF) and half moiety of TTF substituted with one (or two) hydroxymethyl group(s) are described. Their good pi-donating ability is demonstrated by cyclic voltammetry.

  DOI：

  10.1016/s0040-4039(00)79057-5

文献信息

• Directing the Structures and Collective Electronic Properties of Organic Conductors: The Interplay of π-Overlap Interactions and Hydrogen Bonds
  作者：Karine Heuzé、Marc Fourmigué、Patrick Batail、Enric Canadell、Pascale Auban-Senzier

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2971::aid-chem2971>3.0.co;2-s

  日期：——

  The ethylenedithiotetrathiafulvalene (EDT-TTF) directly functionalized with a primary amido group, which is both a hydrogen bond donor and acceptor group, is prepared from the corresponding ester. The electron-donating ability of EDT-TTF-CONH2 (1), which is comparable to that of bisethylenedithiotetrathiofulvalene (BEDT-TTF) despite the presence of the electron-withdrawing amidic group, allows the successful electrocrystallization of air-stable cation radical salts. Two completely different salts are obtained with the isosteric AsF6- and ReO4- ions; the former has 6:1 stoichiometry, and the latter has 2:1 stoichiometry. Compound (1)(6)(AsF6) crystallizes in the P (3) over bar space group, and the three crystallographically independent donor molecules are linked to each other through a combination of N-H ... O and C-H ... O hydrogen bonds. This strong trimeric motif organizes around the AsF6- ion located on the (3) over bar axis, exemplifying the templating effect of the octahedral anion on the whole structure. The presence of a uniform spin chain, as identified in the crystal structure, is confirmed by the Bonner-Fischer behavior of the magnetic susceptibility. In the 2:1 ReO4- salt, two crystallographically independent organic slabs are interconnected through N-H ... O(Re) hydrogen bonds, demonstrating the overlooked hydrogen-bond acceptor capability of this anion. The salt exhibits metallic behavior with a weak localization below 200 K. Both structures reveal the occurrence of a strong C-H ... O hydrogen bond involving the aromatic CH group of the EDT-TTF core, which is activated by the neighboring amidic moiety. Together with the NH ... O hydrogen bond, it gives rise to a cyclic motif noted R-2(1)(7) in Etter's graph set analysis.