r-2-thiomethyl-t-4,t-6-dimethyl-1,3-dithiane | 135559-00-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: r-2-thiomethyl-t-4,t-6-dimethyl-1,3-dithiane
• 英文别名: 4t,6t-dimethyl-2r-(methylthio)-1,2-dithiane
• CAS: 135559-00-1
• 化学式: C₇H₁₄S₃
• 分子量: 194.386
• InChiKey: PSTUAUJXBFMPEO-ZMONIFLSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  r-2-thiomethyl-t-4,t-6-dimethyl-1,3-dithiane 在 乙基2-羟乙基硫醚 作用下， 以 gas 为溶剂， 生成 cis-4,6-dimethyl-1,3-dithian-2-yl cation
  参考文献：
  名称：

  Stereoelectronic effects in ionization reactions of cyclic ortho thioesters

  摘要：

  The objective of this work was to determine whether stereoselectivity observed in certain condensed-phase ionic reactions of ortho thioesters was also evident in related gas-phase reactions. Ionization of the C-2 epimers of cis-4,6-dimethyl-2-(methylthio)-1,3-dithianes 6 and 7 under FT-ICR conditions produced gaseous ions of m/z 147 corresponding to the cis-4,6-dimethyl-1,3-dithian-2-yl cation. Kinetics of ionization were followed by using mixtures of each epimer with 2-methylpropane or with 2-(ethylthio)ethanol. Kinetic parameters were calculated from the rates of decay of the precursor ions (m/z 43 from 2-methylpropane and m/z 75 from 2-(ethylthio)ethanol) at different pressures of reactants. Within experimental error, the specific rates of reaction of each epimer with m/z 43 and with m/z 75 were equal. Ionization is not therefore sensitive to stereochemical configuration at the C-2 reaction site in the gas phase. Solution-phase methylthiolation and methylation of the equatorial epimer (4c,6c-dimethyl-2r-(methylthio)-1,3-dithiane, 7) led to reversible cleavage at C-2 to produce the cis-4,6-dimethyl-1,3-dithian-2-yl cation. Addition of sodium methanethiolate quenched the equilibrium and led irreversibly to a mixture of epimers 6 and 7 in which the axial epimer 6 was in modest excess. The control of reaction stereoselectivity in the formation and trapping of 1,3-dithian-2-yl cations from ortho thioesters is discussed.

  DOI：

  10.1021/jo00019a009
• 作为产物：
  描述：

  r-2-thiomethyl-c-4,c-6-dimethyl-1,3-dithiane 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以50%的产率得到r-2-thiomethyl-t-4,t-6-dimethyl-1,3-dithiane
  参考文献：
  名称：

  2位取代的1，3-二硫杂环丁烷中异头作用的研究

  摘要：

  几个2-取代的1，3-二硫杂环丁烷的构象分析使SCY异头相互作用的评估成为可能，其中Y = SCH 3，SC 6 H 5，CO 2 CH 3，CO 6 H 5，CO 2 H和N（CH 3）2。可以用偶极/偶极和两电子稳定相互作用（立体电子效应）的综合影响来解释对这些基团[ΔG°二噻吩（Y）-ΔGδ环己烷（Y）]观察到的相对影响强度。

  DOI：

  10.1016/s0040-4020(01)87344-0

文献信息

• Stereoconservative protodesilylation of substituted silyl dithianes
  作者：Vanda Cerè、Antonella Capperucci、Alessandro Degl’Innocenti、Salvatore Pollicino

  DOI：10.1016/j.tetlet.2006.08.078

  日期：2006.10

  Protodesilylaton of substituted silyl dithianes occurs with clean retention of configuration. In the case of the 2-phenyl derivative, epimerization of C-2 occurs. Selective functionalization of 2,2-bis trimethylsilyl derivatives can be efficiently obtained. (c) 2006 Elsevier Ltd. All rights reserved.
• JUARISTI, E.;TAPIA, J.;MENDEZ, R., TETRAHEDRON, 1986, 42, N 5, 1253-1264
  作者：JUARISTI, E.、TAPIA, J.、MENDEZ, R.

  DOI：——

  日期：——