5-tert.-butyl-1,3-dithiane | 60311-36-6

• 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: 5-tert.-butyl-1,3-dithiane
• 英文别名: 5-tert-Butyl-1,3-dithiane；5-t-butyl-1,3-dithiane；5-tert.-Butyl-1,3-dithian
• CAS: 60311-36-6
• 化学式: C₈H₁₆S₂
• 分子量: 176.347
• InChiKey: OIDAEEGMNHYBOZ-UHFFFAOYSA-N

物化性质

• 沸点：
  242.6±23.0 °C(Predicted)
• 密度：
  1.027±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  10
• 可旋转键数：
  1
• 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：

  5-tert.-butyl-1,3-dithiane 在 正丁基锂 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 15.0h， 生成 meso-5-tert-butyl-2-(9H-fluoren-9-ylidene)-1,3-dithiane 1,3-dioxide
  参考文献：
  名称：

  1,3-二噻烷的构象约束氧化物：合成和核磁共振光谱研究

  摘要：

  1,3-二噻烷的构象受限衍生物（5-叔丁基-和4,6-二甲基-1,3-二噻烷和二噻烷）已被各种氧化剂氧化，生成轴向和赤道亚砜、二亚砜和砜。轴向亚砜是通过将亲核氢氧化物加成到相应的 2-亚烷基衍生物上并随后进行反羟醛型消除来制备的。正如 DFT 计算所证明的那样，反应结果与衍生物的相对能量有关。分析所得化合物的NMR光谱数据以鉴定4J偶联。发现无论在各自的 C-H 部分之间是否存在轴向或赤道亚砜、硫化物或砜基团，都只能观察到 4J W 耦合。

  DOI：

  10.1002/ejoc.201200675
• 作为产物：
  描述：

  二甲醇缩甲醛 、 2-tert-Butyl-1,3-propanedithiol 以90.4%的产率得到5-tert.-butyl-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

文献信息

• Catalytic Asymmetric Oxidation of Cyclic Dithioacetals: Highly Diastereo- and Enantioselective Synthesis of the <i>S</i>-Oxides by a Chiral Aluminum(salalen) Complex
  作者：Junichi Fujisaki、Kenji Matsumoto、Kazuhiro Matsumoto、Tsutomu Katsuki

  DOI：10.1021/ja106877x

  日期：2011.1.12

  The reaction of nonsubstituted 1,3-dithiane also proceeded in a highly enantioselective manner to give the monoxide with a small formation of the trans-1,3-dioxide, an overoxidation product. Five-membered 1,3-dithiolanes and seven-membered 1,3-dithiepanes also underwent oxidation to give monoxides with high diastereo- and enantioselectivity. It was found that the equilibrium between the two chairlike

  铝 (salalen) 配合物 1 [salalen = 半还原的 salen, salen = N,N'-亚乙基双 (salicylideneiminato)] 被发现是在 30% 过氧化氢存在下不对称氧化环状二硫缩醛的高效催化剂氧化剂。在一系列带有烷基、烯基、炔基和芳基作为取代基的 2-取代 1,3-二噻烷反应中，以高产率获得了反式一氧化物，其比例为 19:1 → >20:1 dr（非对映异构体）。比率）和 98-99% ee（对映异构体过量）。未取代的 1,3-二噻烷的反应也以高度对映选择性的方式进行，得到一氧化物，同时生成少量反式-1,3-二氧化物，这是一种过度氧化产物。五元1,3-二硫戊环和七元1，3-二硫杂环庚烷也经过氧化得到具有高非对映选择性和对映选择性的一氧化物。发现二噻烷的两个椅状构象异构体之间的平衡与在第一次氧化过程中观察到的非对映选择性有关，1,3-二噻烷氧化过程中的
• 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。
• Novel heterocyclic pesticidal compounds
  申请人：THE WELLCOME FOUNDATION LIMITED

  公开号：EP0294228A2

  公开（公告）日：1988-12-07

  The present invention provides a class of novel substituted dithianes which have pesticidal activity, particularly against arthropod pests. Pesticidal formulations containing the compounds of the formula (I), their use in the control of pests and methods for their preparation are also disclosed.

  本发明提供了一类具有杀虫活性，特别是对节肢动物害虫具有杀虫活性的新型取代二噻烷。本发明还公开了含有式（I）化合物的杀虫制剂、其在防治害虫中的用途及其制备方法。
• Synthesis and Conformational Behavior of 2-Phosphonio- and 2-Phosphinyl-1,3-dithianes. Operation of the Generalized Anomeric Effect in the S-C-P+ System
  作者：Marian Mikolajczyk、Piotr P. Graczyk

  DOI：10.1021/jo00121a043

  日期：1995.8

  A stereoselective preparation of various 2-phosphinyl- and 2-phosphonio-1,3-dithianes by desulfurization of the appropriate 2-thiophosphoryl-1,3-dithianes was described. The structure of the title compounds was studied by means of H-1, C-13, and P-31 NMR methods. Configurational assignments were also based on chemical correlation and X-ray structure determination. Both the NMR studies of conformationally labile models and equilibration of diastereomeric compounds showed an increased preference of the phosphinyl and phosphonium groups for the axial orientation. Magnitude of the anomeric effect found varies in the range from ca. 6 kJ/mol in phosphines to more than 10 kJ/mol in phosphonium salts. The anomeric effect could stem from the n(s)-sigma*(c-p) hyperconjugative interaction. If phenyl groups are connected with phosphorus, overlap repulsion involving lone electron pairs of the endocyclic sulfur atoms and pi-electrons of phenyl rings should also be taken into account. The reverse anomeric effect was not observed. No manifestation of the exo anomeric effect in 2-phosphinyl-1,3-dithianes was found.
• Mikolajczyk Marian, Graczyk Piotr P., Wieczorek Michal W., J. Org. Chem, 59 (1994) N 7, S 1679-1693
  作者：Mikolajczyk Marian, Graczyk Piotr P., Wieczorek Michal W.

  DOI：——

  日期：——