1,3-Thiaselenole-2-selone | 53555-45-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 1,3-Thiaselenole-2-selone
• CAS: 53555-45-6
• 化学式: C₃H₂SSe₂
• 分子量: 228.035
• InChiKey: YVJVQXFYNMDMPR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.51
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  zinc(II) chloride 、 四苯基溴化膦 、 1,3-Thiaselenole-2-selone 、 selenium 在 buthyllithium 、 diisopropylamine 作用下， 以 四氢呋喃 为溶剂， 以47%的产率得到bis(tetraphenylphosphonium)-bis(1,3-thiaselenole-2-selone-4,5-diselenolato)-zincate
  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
• 作为产物：
  描述：

  1,3-Thiaselenole-2-morpholinium fluorosulfonate 在 selenium 、 碳酸氢钠 作用下， 以 甲醇 、 水 为溶剂， 以52.6%的产率得到1,3-Thiaselenole-2-selone
  参考文献：
  名称：

  Synthesis of sym-(E/Z)-diselenadithiafulvalene

  摘要：

  DOI：

  10.1021/jo01301a018

文献信息

• LAKSHMIKANTAHM M. V.; CAVA P., J. ORG. CHEM., 1980, 45, NO 13, 2632-2636
  作者：LAKSHMIKANTAHM M. V.、 CAVA P.

  DOI：——

  日期：——
• Neue selenreiche 1,3-Dichalkogenol-2-selone via 4,5-Dilithio-1,3-dichalkogenol-2-selone
  作者：Helmut Poleschner、Reiner Radeglia、Joachim Fuchs

  DOI：10.1016/0022-328x(92)83086-w

  日期：1992.4

  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.
• Synthesis of sym-(E/Z)-diselenadithiafulvalene
  作者：M. V. Lakshmikantham、Michael P. Cava

  DOI：10.1021/jo01301a018

  日期：1980.6