2,2,5,5-Tetraethyl-3,4-dithiahexane-1,6-diol | 159982-41-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 有机二硫化物
• 英文名称: 2,2,5,5-Tetraethyl-3,4-dithiahexane-1,6-diol
• 英文别名: 2-Ethyl-2-[3-(hydroxymethyl)pentan-3-yldisulfanyl]butan-1-ol
• CAS: 159982-41-9
• 化学式: C₁₂H₂₆O₂S₂
• 分子量: 266.469
• InChiKey: PZCRXKPJGMGORG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  91.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2,5,5-Tetraethyl-3,4-dithiahexane-1,6-diol 在 Shi's ketone 、 edetate disodium 吡啶 、 4-二甲氨基吡啶 、 Oxone 、 四丁基硫酸氢铵 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 60.0h， 生成 [2-[(S)-3-(acetyloxymethyl)pentan-3-ylsulfinyl]sulfanyl-2-ethylbutyl] acetate
  参考文献：
  名称：

  Enantioselective Organocatalytic Oxidation of Functionalized Sterically Hindered Disulfides

  摘要：

  The first study on enantioselective oxidation of functionalized sterically hindered disulfides is reported. This study shows that the Shi organocatalytic system using carbohydrate-derived ketone with oxone is superior to the Ellman-Bolm vanadium catalyst in terms of chemical yield and enantioselectivity. Whereas the latter system afforded mostly racemic thiosulfinates in low to moderate yields, the former one afforded thiosulfinates with up to 96% ee.

  DOI：

  10.1021/ol070056z
• 作为产物：
  描述：

  2-乙基丁醛 在 二氯化二硫 、 sodium tetrahydroborate 作用下， 以 四氯化碳 、 乙醇 为溶剂， 反应 19.0h， 生成 2,2,5,5-Tetraethyl-3,4-dithiahexane-1,6-diol
  参考文献：
  名称：

  New Thionitrites: Synthesis, Stability, and Nitric Oxide Generation

  摘要：

  In order to study the influence of substitutions at the alpha and beta carbon atoms on the stability of the S-NO bond, water-soluble thionitrites RSNO have been synthesized by nitrosation of cysteamine and mercaptoethanol derivatives and characterized. H-1 and C-13 NMR spectroscopies have proven to be excellent probes for the nitrosation of thiols. In water, at physiological pH, the compounds decomposed into nitric oxide NO and the corresponding disulfides. The rate at which NO was released was very sensitive to modifications at the alpha and beta carbon atoms. Tertiary thionitrites were more stable than primary thionitrites. The beta-substituents decreased the rates of decomposition in the following order: OH > NHCOCH3 > NH3+. S-Nitrosocysteamine derivatives were greatly stabilized at low pH. The compounds described here might be convenient and useful as vehicles for spontaneous generation of nitric oxide in biological systems, at rates that can be finely tuned and controlled over a wide range.

  DOI：

  10.1021/jo00102a028

文献信息

• New Thionitrites: Synthesis, Stability, and Nitric Oxide Generation
  作者：Beatrice Roy、A. du Moulinet d'Hardemare、Marc Fontecave

  DOI：10.1021/jo00102a028

  日期：1994.11

  In order to study the influence of substitutions at the alpha and beta carbon atoms on the stability of the S-NO bond, water-soluble thionitrites RSNO have been synthesized by nitrosation of cysteamine and mercaptoethanol derivatives and characterized. H-1 and C-13 NMR spectroscopies have proven to be excellent probes for the nitrosation of thiols. In water, at physiological pH, the compounds decomposed into nitric oxide NO and the corresponding disulfides. The rate at which NO was released was very sensitive to modifications at the alpha and beta carbon atoms. Tertiary thionitrites were more stable than primary thionitrites. The beta-substituents decreased the rates of decomposition in the following order: OH > NHCOCH3 > NH3+. S-Nitrosocysteamine derivatives were greatly stabilized at low pH. The compounds described here might be convenient and useful as vehicles for spontaneous generation of nitric oxide in biological systems, at rates that can be finely tuned and controlled over a wide range.
• Enantioselective Organocatalytic Oxidation of Functionalized Sterically Hindered Disulfides
  作者：Noureddine Khiar、Siham Mallouk、Victoria Valdivia、Khalid Bougrin、Mohammed Soufiaoui、Inmaculada Fernández

  DOI：10.1021/ol070056z

  日期：2007.3.1

  The first study on enantioselective oxidation of functionalized sterically hindered disulfides is reported. This study shows that the Shi organocatalytic system using carbohydrate-derived ketone with oxone is superior to the Ellman-Bolm vanadium catalyst in terms of chemical yield and enantioselectivity. Whereas the latter system afforded mostly racemic thiosulfinates in low to moderate yields, the former one afforded thiosulfinates with up to 96% ee.