2-[Bis(5-formyl-2-thienyl)methylen]-1,3-dithiol-4,5-dicarbonitril | 389130-85-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 2-[Bis(5-formyl-2-thienyl)methylen]-1,3-dithiol-4,5-dicarbonitril
• 英文别名: 2-[Bis(5-formylthiophen-2-yl)methylidene]-2H-1,3-dithiole-4,5-dicarbonitrile；2-[bis(5-formylthiophen-2-yl)methylidene]-1,3-dithiole-4,5-dicarbonitrile
• CAS: 389130-85-2
• 化学式: C₁₆H₆N₂O₂S₄
• 分子量: 386.5
• InChiKey: KROAPBCNUUHDGZ-UHFFFAOYSA-N

物化性质

• 沸点：
  585.5±50.0 °C(Predicted)
• 密度：
  1.62±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  189
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  双(2-噻吩)酮 在 劳森试剂 、 三苯基膦 、 三氯氧磷 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 10.0h， 生成 2-[Bis(5-formyl-2-thienyl)methylen]-1,3-dithiol-4,5-dicarbonitril
  参考文献：
  名称：

  Annulenoide Tetrathiafulvalene:, 5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydrotetraepoxy- und 5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydrotetraepithio[22]annulene(2.1.2.1)

  摘要：

  The title compounds are among the first tetrathiafulvalenes with annulene spacers, here with tetraepoxy-[22]annulene(2.1.2.1) (see 3a), tetraepithio[22]annulene(2.1.2.1) (see 3b), and diepithiodiepoxy[22]annulene(2.1.2.1) (see 23) units. The annulenoid tetrathiafulvalenes 3a and 3b are prepared by cyclizing McMurry coupling of the 5,5'-(1,3-benzodithiol-2-ylidenemethylene)bis[furan- or thiophene-2-carbaldehydes] (8a or 8b, resp.) or by Wittig reaction of (1,3-benzodithiol-2-yl)tributylphosphonium tetra fluoroborate (13b) with tetraepoxy[22]annulene(2.1.2.1)-1,12-dione 20 (formation of 3a) or diepithiodiepoxy[22]annulene(2.1.2.1)1,12-dione 22 (formation of 23). The annulenoide tetrathiafulvalene 3a is obtained as a mixture of the isomers (E,E)- and (Z,Z)-3a. At 130 degrees, (Z,Z)-3a rearranges quantitatively into the (E,E)-isomer. Isomer (E,E)-3a is a dynamic molecule, where the (E)-ethene-1,2-diyl bridges rotate around the adjacent sigma -bonds, The tetraepithioannulene derivative 3b as well as 23 only exist in the (Z,Z) -configuration. The oxidation of (E,E/Z,Z)-3a with Br-2 yields the annulene -bridged tetrathiafulvalene dication (E,E)-3a(Ox), while with 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (DDQ) obviously only the radical cation 3a(Sem) is formed, which belongs to the class of cyanine-like violenes. The annulenoide tetrathiafulvalenes 3b and 23, which exist only in the (Z,Z) -configuration, obviously for steric reasons, cannot be oxidized by DDQ. Electrochemical studies are in agreement with these results.

  DOI：

  10.1002/1522-2675(20010815)84:8<2220::aid-hlca2220>3.0.co;2-1

文献信息

• Annulenoide Tetrathiafulvalene:, 5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydrotetraepoxy- und 5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydrotetraepithio[22]annulene(2.1.2.1)
  作者：Gottfried Märkl、Dirk Bruns、Harald Dietl、Peter Kreitmeier

  DOI：10.1002/1522-2675(20010815)84:8<2220::aid-hlca2220>3.0.co;2-1

  日期：2001.8.15

  The title compounds are among the first tetrathiafulvalenes with annulene spacers, here with tetraepoxy-[22]annulene(2.1.2.1) (see 3a), tetraepithio[22]annulene(2.1.2.1) (see 3b), and diepithiodiepoxy[22]annulene(2.1.2.1) (see 23) units. The annulenoid tetrathiafulvalenes 3a and 3b are prepared by cyclizing McMurry coupling of the 5,5'-(1,3-benzodithiol-2-ylidenemethylene)bis[furan- or thiophene-2-carbaldehydes] (8a or 8b, resp.) or by Wittig reaction of (1,3-benzodithiol-2-yl)tributylphosphonium tetra fluoroborate (13b) with tetraepoxy[22]annulene(2.1.2.1)-1,12-dione 20 (formation of 3a) or diepithiodiepoxy[22]annulene(2.1.2.1)1,12-dione 22 (formation of 23). The annulenoide tetrathiafulvalene 3a is obtained as a mixture of the isomers (E,E)- and (Z,Z)-3a. At 130 degrees, (Z,Z)-3a rearranges quantitatively into the (E,E)-isomer. Isomer (E,E)-3a is a dynamic molecule, where the (E)-ethene-1,2-diyl bridges rotate around the adjacent sigma -bonds, The tetraepithioannulene derivative 3b as well as 23 only exist in the (Z,Z) -configuration. The oxidation of (E,E/Z,Z)-3a with Br-2 yields the annulene -bridged tetrathiafulvalene dication (E,E)-3a(Ox), while with 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (DDQ) obviously only the radical cation 3a(Sem) is formed, which belongs to the class of cyanine-like violenes. The annulenoide tetrathiafulvalenes 3b and 23, which exist only in the (Z,Z) -configuration, obviously for steric reasons, cannot be oxidized by DDQ. Electrochemical studies are in agreement with these results.