2-(Tributyl-λ⁵-phosphanylidene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester | 68629-93-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2-(Tributyl-λ⁵-phosphanylidene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 2-(tributyl-lambda5-phosphanylidene)-1,3-dithiole-4,5-dicarboxylate；dimethyl 2-(tributyl-λ5-phosphanylidene)-1,3-dithiole-4,5-dicarboxylate
• CAS: 68629-93-6
• 化学式: C₁₉H₃₃O₄PS₂
• 分子量: 420.574
• InChiKey: SXCCGEDBYCTPMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  26
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-(Tributyl-λ⁵-phosphanylidene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 2.0h， 生成 2-(5-[1,3]Dithiol-2-ylidenemethyl-furan-2-ylmethylene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  2,5-Bis(1,4-dithiafulven-6-yl) furans, thiophenes and N-methyl pyrroles as extended analogues of tetrathiafulvalene

  摘要：

  The title compounds are synthesized by Wittig or Wittig-Horner reactions between the corresponding furan, thiophen and N-methyl-pyrrole-2,5-dicarbaldehydes and P-reagents W or P bearing the 1,3-dithiol-2-ylidene moiety adequately substituted al the 4,5-positions; thanks to usual and thin layer cyclic voltammetry, they are shown to possess good pi-donor abilities.

  DOI：

  10.1016/s0040-4039(00)79014-9
• 作为产物：
  描述：

  [4,5-Bis(methoxycarbonyl)-1,3-dithiol-2-yl](tributyl)phosphonium tetrafluoroborate 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 生成 2-(Tributyl-λ⁵-phosphanylidene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  整个四硫富瓦烯核的π共轭：扩展的四硫富瓦烯衍生物的合成及其异常电化学性能的理论分析

  摘要：

  已经制备了一系列带有一个或两个1，4-二硫富富翁-6基取代基的扩展的四硫富瓦烯（TTF）衍生物。与其他TTF衍生物相比，这些新化合物具有显着的电化学奇异性，这些奇异性受横向杂环取代性质的强烈影响。这种不寻常的电化学行为遵循平方方案序列，并且归因于供体pi分子氧化后的结构变化。电化学数据的数字模拟已用于得出平方方案中涉及的动力学和热力学常数的值。理论计算确定了高度离域的共振形式的重要贡献，该共振形式涉及氧化物种中的四价硫，这可以证明发生不同于TTF的电化学行为。最后，给出了其中两个系统的三级磁化率chi 3，其中给电子和吸电子取代基共存并通过TTF pi系统共轭。

  DOI：

  10.1002/(sici)1521-3765(20000403)6:7<1199::aid-chem1199>3.3.co;2-7

文献信息

• Oxidation of furans with dimethyldioxirane. Interception of malealdehyde and related aldehydes via Wittig reactions
  作者：Brian J. Adger、Collette Barrett、Joseph Brennan、Peter McGuigan、M. Anthony McKervey、Brian Tarbit

  DOI：10.1039/c39930001220

  日期：——

  Unsaturated aldehydes including malealdehyde, generated in acetone by oxidation of furans with dimethyldioxirane, can be trapped efficiently by phosphoranes in Wittig reactions.

  在二甲基二氧杂环丙烷作用下，由呋喃氧化生成的包括马来醛在内的不饱和醛，可通过磷鎓盐参与的维蒂希反应得到有效捕获。
• Conjugation-Extended Tetrathiafulvalene Analogues Involving a Central Aromatic 5-Membered Heterocyclic Linking Group
  作者：Kazuko Takahashi、Takayasu Nihira、Masaaki Yoshifuji、Kensuke Tomitani

  DOI：10.1246/bcsj.66.2330

  日期：1993.8

  Conjugation-extended tetrathiafulvalene analogues, 2,5-bis(1,4-dithiafulven-6-yl)thiophene (2a), 2,5-bis[2,3-bis(methoxycarbonyl)-1,4-dithiafulven-6-yl]thiophene, and 2,5-bis(1,4-dithiafulven-6-yl)furan, involving an aromatic heterocyclic linking group have been synthesized by the Wittig condensation reaction of 2,5-thiophene- and 2,5-furandicarbaldehydes with 1,3-dithiol-2-ylidenetributylphosphorane and its 4,5-bis(methoxycarbonyl) derivative. The electrochemical redox properties of these compounds in solution have been investigated by cyclic voltammetry in order to evaluate the effect of the linking group on the donating ability and the thermodynamic stability of the radical cations. Whereas the radical cations are not so stable, complexes of 2a with 2,3-dichloro-5,6-dicyano-p-benzoquinone and iodine were found to show relatively high conductivities ((1.0—1.1) × 10−3 S cm−1) on a compressed pellet at room temperature.

  2,5-双(1,4-二硫杂富烯-6-基)噻吩(2a)、2,5-双[2,3-双(甲氧基羰基)-1,4-二硫杂富烯-6-基]噻吩和 2,5-双(1,4-二硫杂富烯-6-基)呋喃的共轭扩展四硫杂富烯类似物、通过 2,5- 噻吩和 2,5- 呋喃二羰基醛与 1,3- 二硫醇-2-亚基四丁基磷烷及其 4,5- 双（甲氧基羰基）衍生物的维蒂希缩合反应，合成了涉及芳香杂环连接基团的 2,5- 噻吩和 2,5-呋喃二羰基醛。通过循环伏安法研究了这些化合物在溶液中的电化学氧化还原特性，以评估连接基团对自由基阳离子的捐献能力和热力学稳定性的影响。2a 与 2,3-二氯-5,6-二氰基对苯醌和碘的配合物在室温下的压缩颗粒上显示出相对较高的电导率（(1.0-1.1) × 10-3 S cm-1），而自由基阳离子则不太稳定。
• Dendralene-Type TTF Vinylogs Containing a 1,3-Diselenole Ring
  作者：Ramiya R. Amaresh、Dezhong Liu、Tatyana Konovalova、M. V. Lakshmikantham、Michael P. Cava、Lowell D. Kispert

  DOI：10.1021/jo010663e

  日期：2001.11.1

  2-Diformylmethylene-1,3-diselenole was prepared and condensed with dithiolium phoshonium bromides and dithiolium phosphonates in the presence of base to give dendralene-type vinylogs of TTF bearing a 1,3-diselenole moiety. The electrochemistry of these dendrimers was studied. SEEPR measurements were also carried out. Calculations were carried out on the radical cations and correlated with the EPR values

  制备2-二甲酰基亚甲基-1，3-二硒代苯并与二硫鎓溴化膦和二硫代膦酸酯在碱存在下缩合，得到带有1，3-二硒代烯部分的TTF的树枝状烯丙基乙烯基。研究了这些树枝状大分子的电化学。还进行了SEEPR测量。对自由基阳离子进行了计算并与EPR值相关。
• Synthesis and Electrochemical Properties of Highly Extended and Sulfur-Rich Vinylogs of Tetrathiafulvalene
  作者：Pierre Frère、Kamal Boubekeur、Michel Jubault、Patrick Batail、Alain Gorgues

  DOI：10.1002/1099-0690(200110)2001:19<3741::aid-ejoc3741>3.0.co;2-0

  日期：2001.10

  Using the reactivity of the carbonyl groups of 4,5-diformyl-1,3-dithiol-2-ylidene-substituted ethanals or ethanones with ylides or phosphonate anions, highly extended analogs of TTF 1 and 2 were synthesized by Wittig or Wittig−Horner reactions. Their excellent π-donor properties, as well as the possibility of obtaining polycationic states, were confirmed by cyclic voltammetry. The structural study

  利用4,5-二甲酰基-1,3-二硫醇-2-亚乙基取代的乙醛或乙酮与羰基或膦酸根阴离子的羰基反应性，由WiTTig或WiTTig-Horner合成了TTF 1和2的高度延伸的类似物反应。通过循环伏安法证实了其优异的π-给体性能以及获得聚阳离子态的可能性。阳离子自由基盐1bβγ·PF 6的结构研究揭示了固态的二维网络。
• Cycloaddition of acetylenedicarbaldehyde monoacetal and 2,4,5-trithioxo-1,3-dithiole: Ready access to novel highly extended and sulfur-rich analogues of tetrathiafulvalene (TTF)
  作者：Philippe Leriche、Alain Gorgues、Michel Jubault、Jan Becher、Jesús Orduna、Javier Garin

  DOI：10.1016/0040-4039(95)00014-4

  日期：1995.2

  Thiones 2(′), 4(′) and 3(′) are readily prepared from title compounds. Bis-olefinations of 3 with Akiba's reagents W or H afford 8 which can cyclize into 9 upon acid areatment. (i-PrO)3P mediated coupling of 4 with 5′ affords 7 whose formolysis in 10 and bis-olefination with W or H yields target compound 1. The π-donor ability and stability of 8 and 1 are discussed.

  由标题化合物易于制备亚硫醚2（'），4（'）和3（'）。的双烯化反应3与秋叶的试剂W¯¯或ħ得到8，其可环化到9在酸areatment。（我-Pro）3 P间接的耦合4与5'得到7，其在formolysis 10和双烯与W¯¯或ħ得到目标化合物1。8和1的π供体能力和稳定性 讨论。