trans-(4S,6R)-dimethyl-1,3-dithiane | 22452-23-9

• 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: trans-(4S,6R)-dimethyl-1,3-dithiane
• 英文别名: cis-4,6-dimethyl-1,3-dithiane；cis-4,6-Dimethyl-1,3-dithian；meso-4,6-dimethyl-1,3-dithiane；(4S,6R)-4,6-dimethyl-1,3-dithiane
• CAS: 22452-23-9
• 化学式: C₆H₁₂S₂
• 分子量: 148.293
• InChiKey: HHQVPMWNEKBAJZ-OLQVQODUSA-N

物化性质

• 沸点：
  211.2±23.0 °C(Predicted)
• 密度：
  1.019±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-(4S,6R)-dimethyl-1,3-dithiane 在 sodium methylate 正丁基锂 、 四甲基乙二胺 作用下， 以 甲醇 、 苯 为溶剂， 生成 r-2--t-4-t-6-dimethyl-1,3-dithiane
  参考文献：
  名称：

  Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect

  摘要：

  The operation of the anomeric effect in all the title compounds studied was found. The magnitude of the anomeric effect was found to be larger than 10 kJ/mol. Crystallographic, spectroscopic, and thermodynamic data suggest that the n(S)-sigma*(C-P) hyperconjugative interaction is one of the factors responsible for the anomeric effect. The second interaction stabilizing the axial position of phosphorus can be P=Y...H(4 or 6) hydrogen bond formation. Some other interactions are also possible, namely sigma(C(4,6)-S)-sigma*(C(2)-P) (preferring the equatorial position of phosphorus) and sigma(C(4,6)-S)-pi(P=Y) hyperconjugations and the n(S)-n(Y) repulsions. The latter interaction was also proposed as MO counterpart of lone pair-lone pair repulsions suggested by molecular mechanics calculations. It was proved that various conformation probes can afford different equilibrium constants, if weighted average method and conformationally fixed models are applied. Most of the physical quantities are dependent on the alkyl substitution in the 1,3-dithiane ring. Thus, the relevant procedure for the selection of conformational probe was presented. Since the gamma-effect value in C-13 NMR spectra was found to be very sensitive to the position of a substituent connected with the anomeric carbon atom of 1,3-dithianes, it was applied as a conformational probe. A long range (4)J(C-P) coupling constant in the C-13 NMR spectra and P-31 spin-lattice T-1(DD) relaxation times suggest the existence of close contact(s) between a heteroatom Y(Y=O,S,Se) connected with the axial phosphorus P=Y and axial protons H(4,6) in the 1,3-dithiane ring. Crystallographic data show that the distance from Y to one of these protons is usually much smaller than to the other one and smaller than the sum of H,Y van der Waals radii. The possibility of H..Y hydrogen bond formation is discussed.

  DOI：

  10.1021/jo00086a016
• 作为产物：
  描述：

  乙酰丙酮 在 sodium tetrahydroborate 、 乙醇 、 三氟化硼乙醚 、 乙二胺 、 potassium thioacetate 作用下， 生成 trans-(4S,6R)-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

• Development of a Robust Protocol for the Determination of Weak Acids’ p<i>K</i>_a Values in DMSO
  作者：Sebastian T. Jung、Joachim Podlech

  DOI：10.1021/acs.joc.0c00909

  日期：2020.8.21

  Two methods for the determination of pKa values of weak acids are described, a direct titration with dimsyl potassium in the presence of an indicator and a back-titration in which an analyte/indicator mixture is deprotonated and then titrated with ammonium chloride. Both methods have been validated by measuring pKa values of compounds, for which values had been determined previously. The back-titration

  描述了两种测定弱酸的p K a值的方法，一种是在指示剂存在下用二甲基钾直接滴定，另一种是将分析物/指示剂混合物去质子化然后用氯化铵滴定的反滴定法。两种方法均已通过测量化合物的p K a值进行了验证，此前已确定了该值。采用反滴定法测量了两个1,3-二噻吩衍生的二亚砜和一砜的p K a值。
• Stereoelectronic effects in the gas-phase. 2. Negative ion reactions of 1,3-dithianes and 1,3-dithiane 1-oxides
  作者：Cindy L. Fisher、Scott D. Kahn、Warren J. Hehre、Marjorie C. Caserio

  DOI：10.1021/ja00201a015

  日期：1989.9

  Reactions d'anions gazeux (MeO − , HO − , et electrons thermiques) avec le cis-(dimethyl-4,6) dithiane-1,3 et les oxydes-1 axiaux et equatoriaux correspondants

  反应 d'anions Gazeux (MeO − , H2O − , et electrons thermiques) avec le cis-(dimethyl-4,6) dithiane-1,3 et les oxydes-1 axiaux et euquatoriaux
• Configurationally and conformationally homogeneous cyclic n-aryl sulfimides—IV
  作者：Josef Bailer、Peter K. Claus、Friedrich W. Vierhapper

  DOI：10.1016/0040-4020(80)80041-x

  日期：1980.1

  1,3-Dithiane-1-N-p-chlorophenylimides (1,4-9) were prepared and their configuration and conformation was determined by 1H and 13C NMR. The compounds were rearranged to the corresponding 2-(2'-amino-5'-chlorophenyl)-1, 3-dithianes (1U,4U,9U). The rearrangement reactions took place with ⩾95% stereospecifity. The mechanism of the reaction was investigated with the aid of analogs specifically deuterated

  1,3-二噻烷-1-N- p -chlorophenylimides（1，4 - 9）的制备和它们的配置和构象，通过测定1 H和13 C ^ NMR。将化合物重新排列为相应的2-（2'-氨基-5'-氯苯基）-1，3-二硫烷（1U，4U，9U）。重排反应以reactions95％的立体特异性发生。借助在C-2专门氘化的类似物研究了反应机理。
• Oxidation of Dithia Compounds: Comparative Experimental and Theoretical Studies on 1,3‐Bis(methylthio)propane, Bis(methylthio)methane, and <i>meso</i> ‐4,6‐Dimethyl‐1,3‐dithiane
  作者：Victorino Vallejos González、Joachim Podlech

  DOI：10.1002/ejoc.202100940

  日期：2021.10.21

  influence of the sulfur groups in 1,3-dithia compounds is especially obvious in conformationally constrained 1,3-dithianes. Oxidations with different oxidants are investigated experimentally by NMR spectroscopical analysis and by calculation of activation barriers and stereoelectronic effects by using quantum chemical methods.

  1,3-二硫杂化合物中硫基的相互影响在构象受限的1,3-二噻烷中尤为明显。通过核磁共振光谱分析和使用量子化学方法计算激活势垒和立体电子效应，对不同氧化剂的氧化进行了实验研究。
• Stereoselective Functionalization of Dithiolanes and Dithianes: The First Example of an Axial Trapping
  作者：Alessandro Degl’Innocenti、Salvatore Pollicino、Antonella Capperucci、Vanda Cerè、Tiziano Nocentini

  DOI：10.1055/s-2002-33521

  日期：——

  and dithianes can be easily functionalized under fluoride ion conditions. The functionalization occurs stereoselectively, the products bearing the incoming groups in the position formerly occupied by the silyl moiety. These results lead to the first example of dithiolane and dithiane axial trapping.

  2-Silyl-1,3-dithiolanes 和 dithianes 在氟离子条件下很容易被官能化。官能化立体选择性地发生，产物在先前由甲硅烷基部分占据的位置上带有传入基团。这些结果导致了二硫戊环和二噻烷轴向捕获的第一个例子。