2,3,4,5-Tetrahydro-1,6-dithia-3a-aza-phenalene-8-carbaldehyde | 27674-20-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2,3,4,5-Tetrahydro-1,6-dithia-3a-aza-phenalene-8-carbaldehyde
• 英文别名: 4,10-Dithia-1-azatricyclo[7.3.1.05,13]trideca-5,7,9(13)-triene-7-carbaldehyde
• CAS: 27674-20-0
• 化学式: C₁₁H₁₁NOS₂
• 分子量: 237.346
• InChiKey: XSJCRXWPCHITFO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  70.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,3,4,5-Tetrahydro-1,6-dithia-3a-aza-phenalene-8-carbaldehyde 在 间氯过氧苯甲酸 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 35.0h， 生成
  参考文献：
  名称：

  用富电子单元THDTAP修饰三联吡啶：探索用于识别金属离子的荧光传感器的有效方法

  摘要：

  将供电子单元2,3,4,6-四氢-1,6-二硫代-3a-氮杂苯并菲（THDTAP）引入三联吡啶（TPy）上，得到TPy配体类型的供体-受体（DA）。化合物2）。一旦上的THDTAP部分两个硫原子的选择性氧化2，所述配体3 - 6被创建。的电子结构2 - 6被理论，电化学和光谱研究评价。在硫原子上的氧化带来显著影响上THDTAP部分的给电子能力，随后，导线对的分子内电荷转移（ICT）细调制2 - 6和的复合物的电子激发态2 - 6与金属离子。基于所述光学响应2 - 6朝向金属离子，所述步骤一步识别的Zn 2+，Cd的2+和Ag +离子是通过采用设置2和3作为组合荧光传感器。

  DOI：

  10.1002/cjoc.201900226
• 作为产物：
  描述：

  THDTAP 、 N,N-二甲基甲酰胺 在 三氯氧磷 作用下， 反应 7.0h， 以85%的产率得到2,3,4,5-Tetrahydro-1,6-dithia-3a-aza-phenalene-8-carbaldehyde
  参考文献：
  名称：

  Decorating BODIPY with electron-rich unit THDTAP: An ICT-based fluorometric sensor toward peroxide, acid, and electrochemical stimuli

  摘要：

  A new type of BODIPY dye, compound 2 which possesses donor-acceptor (D-A) type structure, is synthesized by decorating electron-rich THDTAP unit onto the meso-position of BODIPY. The THDTAP has two chemically active sites (S and N atoms) that are utilized to manipulate the optoelectronic properties. By stepwise oxidation of two S-atoms on THDTAP moiety with m-CPBA, the 2 was converted to 3, trans-4, syn-4, 5, and 6. This transformation results in large influence on optoelectronic properties. The theoretical calculations reveal that the LUMOs of 2-6 are all located on BODIPY core, whereas their HOMOs show the different distributions. The 2 and 3 show the intramolecular charge-transfer (ICT) transition as proved by TD-DFT calculations, red-shifts of absorption and emission bands, and solvatochromism. The ICT process is inhibited in trans-4, syn-4, 5, and 6 due to the high oxidation states of S-atoms on THDTAP moieties. As a result, these four compounds display characteristic fluorescence of BODIPY. The femtosecond transient absorption (fs-TA) spectroscopic study reveals that 2 shows photoinduced hole-transfer (PHT) process in dichloromethane (DCM) solution. Upon acidification and neutralization of N-atom on THDTAP moiety, the ICT/PHT process of 2 in DCM is reversibly manipulated to result in fluorescence ON/OFF of BODIPY core. Moreover, the fluorescence of BODIPY core on 2 can be switched on through electrochemical oxidation of N-atom on THDTAP moiety. The compound 2 is thus a promising fluorometric sensor toward peroxide, acid, and electrochemical stimuli.

  DOI：

  10.1016/j.dyepig.2019.04.069