dispiro[adamantane-2,4'-(1,2,3,5,6)-pentathiepane-7',2”-adamantane] | 189503-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: dispiro[adamantane-2,4'-(1,2,3,5,6)-pentathiepane-7',2”-adamantane]
• 英文别名: Dispiro-(adamantan-2,4'-(1,2,3,5,6)pentathiepan-7',2''-adamantan)
• CAS: 189503-06-8
• 化学式: C₂₀H₂₈S₅
• 分子量: 428.772
• InChiKey: KTZJNTGQGSYEEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dispiro[adamantane-2,4'-(1,2,3,5,6)-pentathiepane-7',2”-adamantane] 在 金刚烷-2-硫酮 、 sodium thiophenolate 、 sodium 作用下， 以 氨 、 丙酮 为溶剂， 反应 240.5h， 生成 2,2-bis(benzylthio)adamantane
  参考文献：
  名称：

  The Conversion of Thioketones to 1,2,4,5-Tetrathianes and Its Mechanism

  摘要：

  Thiobenzophenone and adamantanethione react with sulfur (1:1) under catalysis by sodium thiophenoxide in acetone at rt furnishing 1,2,4,5-tetrathianes (9 and 43) in high yields. An attack of the oligothiolate (R-S-x(-)) on the C-atom of drop C=S is proposed as initiating step. Thione S-sulfides (R2C=S+-S-, thiosulfines) cannot be intermediates, since they combine fast with thiones affording 1,2,4-trithiolanes. With more sulfur, adamantanethione produces the 1,2,3,5,6-pentathiepane-bis(spiroadamantane) (44) which interconverts with the tetrathiane, but not with the 1,2,4-trithiolane, in an equilibrium catalyzed by R-S-x(-). According to C-13 NMR evidence, the tetrathianebis(spiroadamantane) occurs in a twist conformation which inverts with Delta G not equal 16.0 kcal mol(-1).

  DOI：

  10.3987/com-96-7706
• 作为产物：
  描述：

  dispiro[adamantane-2,3'-(1,2,4)-trithiolane-5',2'-adamantane] 在 sodium thiophenolate 、 sulfur 作用下， 以 丙酮 为溶剂， 反应 8.0h， 生成 dispiro[adamantane-2,4'-(1,2,3,5,6)-pentathiepane-7',2”-adamantane]
  参考文献：
  名称：

  The Conversion of Thioketones to 1,2,4,5-Tetrathianes and Its Mechanism

  摘要：

  Thiobenzophenone and adamantanethione react with sulfur (1:1) under catalysis by sodium thiophenoxide in acetone at rt furnishing 1,2,4,5-tetrathianes (9 and 43) in high yields. An attack of the oligothiolate (R-S-x(-)) on the C-atom of drop C=S is proposed as initiating step. Thione S-sulfides (R2C=S+-S-, thiosulfines) cannot be intermediates, since they combine fast with thiones affording 1,2,4-trithiolanes. With more sulfur, adamantanethione produces the 1,2,3,5,6-pentathiepane-bis(spiroadamantane) (44) which interconverts with the tetrathiane, but not with the 1,2,4-trithiolane, in an equilibrium catalyzed by R-S-x(-). According to C-13 NMR evidence, the tetrathianebis(spiroadamantane) occurs in a twist conformation which inverts with Delta G not equal 16.0 kcal mol(-1).

  DOI：

  10.3987/com-96-7706

文献信息

• Metallkomplexe mit funktionalisierten Schwefelliganden, XV [1]. Reaktionen von Platin(0)-Komplexen mit 1,2,4-Trithiolanen, 1,2,4,5-Tetrathianen, 1,2,3,5,6-Pentathiepanen sowie Thioketonen. Kristallstrukturanalyse von (Ph₃P)₂Pt(η²-Ph₂C=S) / Metal Complexes of Functionalized Sulfur Containing Ligands, XV [1]. Reactions of Platinum(O) Complexes with 1,2,4-Trithiolanes, 1,2,4,5-Tetrathianes, 1,2,3,5,6-Pentathiepanes as well as Thioketones. X-Ray Structure Analysis of (Ph₃P)₂Pt(η²-Ph₂C=S)
  作者：Wolfgang Weigand、Ralf Wünsch、Christian Robl、Grzegorz Mloston、Heinrich Nöth、Manfred Schmidt

  DOI：10.1515/znb-2000-0601

  日期：2000.6.1

  3,3,5,5-Tetraphenyl-1,2,4-trithiolane (1) reacts with twofold excess of (Ph₃P)₂Pt(η²-C₂H₄) (4) to give a 1:1 mixture of the complexes (Ph₃P)₂ (6a) and (Ph₃P)₂Pt(η²-Ph₂C=S) (7a). Treatment of 3,3,6,6-tetraphenyl-1,2,4,5-tetrathiane (2) with a fourfold excess of 4 yields [Pt₂(PPh₃)₄(μ-S)₂] (8) and the platinum(O) compound 7a. The reaction of the 1,2,3,5,6- pentathiepane 3 with a fourfold excess of 4 affords a 1:1:1 mixture of 8, the platinum(O) complex 7b and the bis-thiolato platinum(II) complex 6b. The thioketone complexes 7a-c were formed in smooth reactions of 4 with the thioketones 5a-c. The molecular structure of (Ph₃P)₂Pt(η²-Ph₂C=S) (7a) has been established by single-crystal X-ray analysis.

  3,3,5,5-四苯基-1,2,4-三硫环戊烷（1）与过量的（Ph3P）2Pt(η2-C2H4)（4）反应，得到复合物（Ph3P）2 （6a）和（Ph3P）2Pt(η2-Ph2C=S)（7a）的1:1混合物。3,3,6,6-四苯基-1,2,4,5-四硫环戊烷（2）与四倍量的4反应产生[Pt2(PPh3)4(μ-S)2]（8）和铂（O）化合物7a。1,2,3,5,6-五硫己烷3与四倍量的4反应产生8、铂（O）配合物7b和双硫代硫醇铂（II）配合物6b的1:1:1混合物。硫酮配合物7a-c是4与硫酮5a-c的顺利反应形成的。 （Ph3P）2Pt(η2-Ph2C=S)（7a）的分子结构已通过单晶X射线分析确定。
• The Fluoride Anion-Catalyzed Sulfurization of Thioketones with Elemental Sulfur Leading to Sulfur-Rich Heterocycles: First Sulfurization of Thiochalcones
  作者：Grzegorz Mlostoń、Jakub Wręczycki、Katarzyna Urbaniak、Dariusz M. Bieliński、Heinz Heimgartner

  DOI：10.3390/molecules26040822

  日期：——

  fluoride anion catalyzed sulfurization of their α,β-unsaturated analogues, i.e., thiochalcones is slow and inefficient. However, an alternative protocol with triphenylphosphine (PPh3) applied as a catalyst, offers an attractive approach to the synthesis of 3H-1,2-dithioles via 1,5-dipolar electrocyclization of the in situ-generated α,β-unsaturated thiocabonyl S-sulfides. All reactions occur under mild

  氟化物阴离子被证明是元素硫 (S 8 ) 的优异活化剂，可对硫酮进行硫化，从而产生多种富硫杂环。由于溶解度问题，反应必须分别在 THF 中使用四丁基氟化铵 (TBAF) 或在 DMF 中使用氟化铯 (CsF) 进行。反应性硫化试剂是原位生成的亲核氟多硫化物阴离子FS (8−x) - ，其根据亲碳加成模式与C=S键反应。由此形成的二硫杂环丙烷与开环形式（双自由基/两性离子）处于平衡状态，是关键的中间体，它们经历逐步二聚化以提供 1,2,4,5-四硫杂环烷或分子内插入，导致以2,2,4,4-四甲基环丁烷-1,3-二酮的硫代衍生物为扩环产物为例。在 TBAF 催化的反应中，水通过 H 桥与氟阴离子结合并由此形成其稳定的水合物，并参与二次反应，例如在 2,2,4,4-四甲基-3-硫代环丁酮的情况下导致形成一些意想不到的产品，例如扩环的二硫内酯和开环的二硫代羧酸酯。与硫酮相比，氟阴离子催化其α,β-