5,5'-(1,3-Benzodithiol-2-ylidenmethylen)bis[furan-2-carbaldehyde] | 389130-86-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 5,5'-(1,3-Benzodithiol-2-ylidenmethylen)bis[furan-2-carbaldehyde]
• 英文别名: 5-[1,3-benzodithiol-2-ylidene-(5-formylfuran-2-yl)methyl]furan-2-carbaldehyde
• CAS: 389130-86-3
• 化学式: C₁₈H₁₀O₄S₂
• 分子量: 354.407
• InChiKey: VGVCGEDJICSSOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.42
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  5,5'-(1,3-Benzodithiol-2-ylidenmethylen)bis[furan-2-carbaldehyde] 在 四氯化钛 、 铜 、 锌 作用下， 以 四氢呋喃 为溶剂， 生成 (1Z,3Z,6Z,8Z,10Z,12Z,14Z,17Z,19Z,21Z)-5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydro-1,4:6,9:12,15:17,20-tetraepoxy[22]annulen 、 (1Z,3Z,6Z,8Z,10E,12Z,14Z,17Z,19Z,21E)-5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydro-1,4:6,9:12,15:17,20-tetraepoxy[22]annulen
  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
• 作为产物：
  描述：

  (1,3-benzodithiol-2-yl)tributylphosphonium tetrafluoroborate 在 potassium tert-butylate 、 三氯氧磷 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 5,5'-(1,3-Benzodithiol-2-ylidenmethylen)bis[furan-2-carbaldehyde]
  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