2-(1-hydroxycyclohexyl)-1,3-dithiane | 5849-22-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(1-hydroxycyclohexyl)-1,3-dithiane
• 英文别名: 1-(<1.3>Dithian-2-yl)-cyclohexanol；2-(1'-Hydroxycyclohexyl-1')-1,3-dithian；1-[1,3]dithian-2-yl-cyclohexanol；1-(1,3-Dithian-2-yl)cyclohexan-1-ol
• CAS: 5849-22-9
• 化学式: C₁₀H₁₈OS₂
• 分子量: 218.384
• InChiKey: JAAKHGVUIVVCFU-UHFFFAOYSA-N

物化性质

• 沸点：
  354.2±42.0 °C(Predicted)
• 密度：
  1.206±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  70.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(1-hydroxycyclohexyl)-1,3-dithiane 在 正丁基锂 、 四丁基氟化铵 、 水 、 calcium carbonate 、 mercury dichloride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 53.75h， 生成 1-(1-hydroxy-cyclohexyl)-hex-2-yne-1,6-diol
  参考文献：
  名称：

  A Highly Efficient Access to Spiroketals, Mono-unsaturated Spiroketals, and Furans: Hg(II)-Catalyzed Cyclization of Alkyne Diols and Triols

  摘要：

  Hg(II) salts are identified as highly efficient catalysts for the versatile construction of spiroketals from alkyne diols in aqueous conditions. Monounsaturated spiroketals and furans were accessed with equal ease when propargylic triols (or propargylic diols) were subjected to similar conditions. Even the semiprotected alkyne diols gave the corresponding spiroketals with the same ease in a cascade manner. The reactions are Instant and high yielding at ambient temperatures. Regioselectivity issues are well addressed.

  DOI：

  10.1021/ol201102x
• 作为产物：
  描述：

  1,3-二噻烷 、 环己酮 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 2-(1-hydroxycyclohexyl)-1,3-dithiane
  参考文献：
  名称：

  An Efficient Photo-SET-Induced Cleavage of Dithiane−Carbonyl Adducts and Its Relevance to the Development of Photoremovable Protecting Groups for Ketones and Aldehydes

  摘要：

  Irradiation of dithiane-aldehyde/ketone adducts in the presence of benzophenone leads to C-C bond cleavage regenerating the carbonyl compounds. It is established that the mechanism of this reaction involves photochemically induced single electron transfer from the dithiane moiety to the excited molecule of ET-photosensitizer, accompanied by mesolytic C-C cleavage in the generated cation-radical, which is assisted by the anion-radical of benzophenone. This mechanism is confirmed by a Hammett plot study of the cleavage in the dithiane adducts of substituted aromatic aldehydes and a deuterium kinetic isotope effect study. Ab initio computations at UHF/6-31G* and MP2/6-31G* levels of theory in conjunction with self-consistent reaction field (self-consistent isodensity-polarized continuum model), to account for the solvent effect, also support the experimental findings. The reaction is most efficient for protection of aromatic aldehydes and ketones and aliphatic ketones, and is a novel method for protecting carbonyl functionalities with a photoremovable group.

  DOI：

  10.1021/jo981697y

文献信息

• Mercuric Chloride and Iodide Mediated Cyclization of Tethered Alkynedithioacetals as a General Route to Five- and Six-Membered Rings:  Tuning of Regioselectivity by Alkyne Substitution
  作者：Goutam Biswas、Subir Ghorai、Anup Bhattacharjya

  DOI：10.1021/ol0527274

  日期：2006.1.1

  Mercuric chloride mediated cyclization of tethered alkynedithioacetals has been established as a general route to five- and six-membered carbocycles and heterocycles. Substitution at the alkyne terminus leads to preferential formation of five-membered rings, whereas unsubstituted alkynedithioacetals give six-membered rings as the major products. Mercuric iodide interrupts the reaction at the intermediate dithioacetal

  [反应：见正文]氯化汞介导的链状炔二硫缩醛的环化已被确立为通向五元和六元碳环和杂环的一般途径。在炔基末端的取代导致优先形成五元环，而未取代的炔二硫缩醛以六元环为主要产物。碘化汞在中间二硫缩醛阶段中断反应。
• Mercury(II) Chloride-Mediated Cyclization−Rearrangement of <i>O</i>-Propargylglycolaldehyde Dithioacetals to 3-Pyranone Dithioketals:  An Expeditious Access to 3-Pyranones
  作者：Subir Ghorai、Anup Bhattacharjya

  DOI：10.1021/ol047893a

  日期：2005.1.1

  O-Propargyl glycolaldehyde dithioacetals undergo a unique cyclization-rearrangement in the presence of mercuric chloride and calcium carbonate to afford 3-pyranones exclusively or along with 2,5-dihydrofuran-3-carboxaldehydes via their dithioketals and dithioacetals.