4,5-bis(benzoylseleno)-1,3-thiaselenol-2-selon | 142182-65-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 4,5-bis(benzoylseleno)-1,3-thiaselenol-2-selon
• CAS: 142182-65-8
• 化学式: C₁₇H₁₀O₂SSe₄
• 分子量: 594.171
• InChiKey: XCMOCCTWJJOCMV-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  苯甲酰氯 、 alkaline earth salt of/the/ methylsulfuric acid 以 丙酮 为溶剂， 反应 0.25h， 以86%的产率得到4,5-bis(benzoylseleno)-1,3-thiaselenol-2-selon
  参考文献：
  名称：

  Neue selenreiche 1,3-Dichalkogenol-2-selone via 4,5-Dilithio-1,3-dichalkogenol-2-selone

  摘要：

  1,3-Dithiole-2-thione (1), 1,3-diselenole-2-selone (2), 1,3-thiaselenole-2-thione (3), 1,3-dithiole-2-selone (4), 1,3-diselenole-2-thione (5) and 1,3-thiaselenole-2-selone (6) are dilithiated with lithium diisopropyl amide in the 4/5 position, followed by selenation (thiolation) and complexation of the resulting heterocyclic diselenolates (dithiolates) to the zinc bis-chelates (tetrabutylammonium or tetraphenylphosphonium salts).These zinc complexes react with benzoyl chloride to the corresponding selenole and thiole esters. It is noteworthy that the heterocyclic thiones with one or two ring selenium atoms undergo ring transformation (Dimroth rearrangement) during the lithiation chalcogenation sequence, whilst the thione sulfur and one ring selenium atom change their places: 3 --> 1,3-dithiole-2-selone-4,5-diselenolate or dithiolate structure, 5 --> 1,3-thiaselenole-2-selone-4,5-diselenolate structure. This observed rearrangement is verified by independent synthetic pathways. The corresponding identical zinc chelates 12 and complex 18 result from the precursors 3 and 4, and 5 and 6, respectively. Trapping experiments support the conclusion that this rearrangement takes place already during lithiation. The zinc chelates and thiole and selenole esters are characterized in detail by IR and above all by C-13 and Se-77 NMR spectroscopy, including NMR shift values of the precursor heterocycles. The X-ray crystal structure determination of bis(tetraphenylphosphonium)-bis(1,3-thiaselenole-2-selone-4,5-diselenolato) zincate (18), obtained from 5, shows the rearrangement of 5 to the 1,3-thiaselenole-2-selone partial structure in 18.

  DOI：

  10.1016/0022-328x(92)83086-w