tetrathiafulvalene-3-carbonyl chloride | 128881-67-4

• 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: tetrathiafulvalene-3-carbonyl chloride
• 英文别名: tetrathiafulvalene-4-carbonyl chloride；tetrathiafulvalene-2-carbonyl chloride；2-(1,3-Dithiol-2-ylidene)-1,3-dithiole-4-carbonyl chloride
• CAS: 128881-67-4
• 化学式: C₇H₃ClOS₄
• 分子量: 266.817
• InChiKey: GUZPWVNOFNWOON-UHFFFAOYSA-N

物化性质

• 熔点：
  122-125 °C (decomp)
• 沸点：
  295.1±40.0 °C(Predicted)
• 密度：
  1.790±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  tetrathiafulvalene-3-carbonyl chloride 在 六氟锑酸亚硝 、 三乙胺 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  Anion complexation by calix[4]arene–TTF conjugates

  摘要：

  Calix[4]arenes bearing tetrathiafulvalene (TTF) moieties appended to the upper rim via the amidic functions were synthesized and used for H-1 NMR and UV/Vis complexation studies towards selected anions. It was found that the complexation affinity towards H2PO4- dramatically depends on the substitution pattern of the calixarene moiety. As a result, the proximally disubstituted derivative has a complexation constant by two orders of magnitude higher than the distally disubstituted analogue. The differences between proximal and distal receptors were also documented by their behaviour during the oxidation of the attached TTF units. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2011.06.001
• 作为产物：
  描述：

  四硫富瓦烯 在 草酰氯 、 N,N-二甲基甲酰胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙腈 、 苯 为溶剂， 反应 2.0h， 生成 tetrathiafulvalene-3-carbonyl chloride
  参考文献：
  名称：

  Anion complexation by calix[4]arene–TTF conjugates

  摘要：

  Calix[4]arenes bearing tetrathiafulvalene (TTF) moieties appended to the upper rim via the amidic functions were synthesized and used for H-1 NMR and UV/Vis complexation studies towards selected anions. It was found that the complexation affinity towards H2PO4- dramatically depends on the substitution pattern of the calixarene moiety. As a result, the proximally disubstituted derivative has a complexation constant by two orders of magnitude higher than the distally disubstituted analogue. The differences between proximal and distal receptors were also documented by their behaviour during the oxidation of the attached TTF units. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2011.06.001

文献信息

• Synthesis of amphiphilic, mono-functionalised tetrathiafulvalenes; X-ray crystal structure of 4-(6-sromohexanoyl)tetrathiafulvalene
  作者：Martin R. Bryce、Graeme Cooke、Ajaib S. Dhindsa、Dominique Lorcy、Adrian J. Moore、Michael C. Petty、Michael B. Hursthouse、A. I. Karaulov

  DOI：10.1039/c39900000816

  日期：——

  Reaction of monolithiated-tetrathiafulvalene (TTF) has been used in the synthesis of amphiphilic TTF derivatives bearing long chains attached through carbon, silicon, sulphur, selenium, and tellurium atoms; the single crystal X-ray structure of the title compound is described.

  单片化四硫富瓦烯（TTF）的反应已用于合成带有通过碳，硅，硫，硒和碲原子连接的长链的两亲性TTF衍生物。描述了标题化合物的单晶X射线结构。
• Synthesis of 4,5-Bis- and 4,4′,5,5′-Tetrakis(2-hydroxyethylthio) tetrathiafulvalene: The Assembly of Tris- and Pentakis(tetrathiafulvalene) Macromolecules
  作者：Gary J. Marshallsay、Thomas K. Hansen、Adrian J. Moore、Martin R. Bryce、Jan Becher

  DOI：10.1055/s-1994-25606

  日期：——

  Efficient syntheses are reported of the novel pentakis- and tris(tetrathiafulvalene) derivatives 11 and 12, respectively, by esterification of tetraol and diol derivatives 8 and 10 with TTF-carbonyl chloride.

  报告通过四元醇和二元醇衍生物 8 和 10 与 TTF-羰酰氯的酯化反应，分别高效合成了新型戊二烯烃和三(四硫杂戊烯)衍生物 11 和 12。
• Synthesis and intramolecular charge-transfer properties of new tetrathiafulvalene–σ-tetracyanoanthraquinodimethane diad (TTF–σ-TCNAQ) and triad (TTF–σ-TCNAQ–σ-TTF) molecules
  作者：Pilar de Miguel、Martin R. Bryce、Leonid M. Goldenberg、Andrew Beeby、Vladimir Khodorkovsky、Lev Shapiro、Angelika Niemz、Alej,ro O. Cuello、Vincent Rotello

  DOI：10.1039/a704013j

  日期：——

  We report the use of functionalised electron acceptor tetracyanoanthraquinodimethane (TCNAQ) units in the synthesis of novel diad D–σ-A compounds 6 and 7 [D=tetrathiafulvalenyl (TTF) and ferrocenyl] and the triad TTF–σ-TCNAQ–σ-TTF assembly 8. Compounds 6–8 display a very weak, broad, low-energy intramolecular charge-transfer band in the UV–VIS spectra. Nanosecond laser flash photolysis of compound 6 did not lead to any new transient absorptions in the 300–800 nm region, suggesting that if a charge-separated species is formed upon excitation, then back electron transfer occurs very rapidly to regenerate the ground state. Cyclic voltammetry of compounds 6–8 shows that reversible oxidation processes occur for the TTF and ferrocene moieties, and a reversible two-electron reduction occurs for the TCNAQ moiety. Spectroelectrochemical studies on compound 6 have enabled the redox processes to be assigned to the sequential formation of the TTF radical cation and dication upon oxidation, and the TCNAQ dianion upon reduction. Simultaneous electrochemistry and EPR (SEEPR) experiments provide further evidence for intramolecular interaction between the TTF and TCNAQ moieties in compound 6. Quantum mechanical calculations on compound 6, performed by the AM1 method, predict that in its minimum energy conformation the TTF and TCNAQ moieties are approximately orthogonal to one another, with the TCNAQ unit folded into a butterfly conformation.

  我们报告了利用官能化电子受体四氰基蒽醌二甲烷（TCNAQ）单元合成新型二元 DâÏ-A 化合物 6 和 7 [D=tetrathiafulvalenyl (TTF) and ferrocenyl] 以及三元 TTFâÏ-TCNAQâÏ-TTF 组合物 8 的情况。化合物 6â8 在紫外可见光谱中显示出非常微弱、宽广、低能的分子内电荷转移带。化合物 6 的纳秒激光闪烁光解并没有在 300â800 nm 区域产生任何新的瞬态吸收，这表明如果在激发时形成了电荷分离的物种，那么回电子转移就会非常迅速地发生，从而重新生成基态。化合物 6â8 的循环伏安法显示，TTF 和二茂铁分子发生了可逆的氧化过程，TCNAQ 分子发生了可逆的双电子还原。通过对化合物 6 的光谱电化学研究，可以确定氧化还原过程是 TTF 自由基阳离子和二阳离子在氧化时依次形成，TCNAQ 二阴离子在还原时依次形成。同时进行的电化学和 EPR（SEEPR）实验进一步证明了化合物 6 中 TTF 和 TCNAQ 分子之间的分子内相互作用。通过 AM1 方法对化合物 6 进行的量子力学计算预测，在其最小能量构象中，TTF 和 TCNAQ 分子近似相互正交，TCNAQ 单元折叠成蝶形构象。
• Langmuir–Blodgett films of a tetrathiafulvalene derivative substituted with an azobenzene group
  作者：Leonid M. Goldenberg、Martin R. Bryce、Stefan Wegener、Michael C. Petty、John P. Cresswell、Igor K. Lednev、Ronald E. Hester、John N. Moore

  DOI：10.1039/a702797d

  日期：——

  The new tetrathiafulvalene derivative1, functionalised with an azobenzene substituent, has been synthesised. Cyclic voltammetric and spectroelectrochemical studies in solution demonstrate the reversible formation of the radical cation of 1. UV–VIS spectroscopy suggests that there is a weak interaction between the TTF and azobenzene moieties in compound 1, and demonstrates that trans–cis isomerisation occurs upon photolysis of the azobenzene substituent. Semi-conducting LB films of 1 have been assembled without the need for added fatty acid: room temperature conductivity values of the films before and after doping with iodine vapour were σrt=10–3–10–5 S cm–1 and 2×10–2–10–3 S cm–1 , respectively. No change in the conductivity of the LB films was observed under irradiation.

  我们合成了一种新的四噻吩衍生物1，该衍生物具有偶氮苯取代基功能。溶液中的循环伏安法和光谱电化学研究表明，1 的自由基阳离子是可逆形成的。紫外可见分光光度法表明，化合物 1 中的 TTF 和偶氮苯分子之间存在微弱的相互作用，并证明偶氮苯取代基光解时会发生反式异构化。在不添加脂肪酸的情况下，1 的半导电枸橼酸薄膜已经形成：掺入碘蒸气之前和之后薄膜的室温电导率值分别为 Ïrt=10â3â10â5 S cmâ1 和 2Ã10â2â10â3 S cmâ1 。在辐照条件下，枸杞薄膜的电导率没有发生变化。
• The first allylic alcohol derivatives of tetrathiafulvalene. A route to new covalently linked donors
  作者：Raquel Andreu、Javier Garín、Jesús Orduna、María Savirón、Santiago Uriel

  DOI：10.1016/0040-4039(95)00749-3

  日期：1995.6

  The first allylic alcohols derived from TTF are described. They afford new multi-stage redox assemblies (6–8), including the first system containing both EDT-TTF and ferrocene moieties (6a).

  描述了衍生自TTF的第一烯丙基醇。他们提供了新的多级氧化还原组件（6-8），包括第一个同时包含EDT-TTF和二茂铁部分的系统（6a）。