meso-2,4-pentanedithiol | 4038-08-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醇
• 英文名称: meso-2,4-pentanedithiol
• 英文别名: meso-2,4-Pentandithiol；2,4-Pentanedithiol；pentane-2,4-dithiol
• CAS: 4038-08-8
• 化学式: C₅H₁₂S₂
• 分子量: 136.282
• InChiKey: WUVMJSSTEMBGRQ-UHFFFAOYSA-N

物化性质

• 沸点：
  67 °C(Press: 12 Torr)
• 密度：
  0.973±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  meso-2,4-pentanedithiol 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：

  2,4-戊二醇 在 吡啶 、 盐酸 、 N,N-二甲基甲酰胺 、 对甲苯磺酰氯 、 锌 、 potassium thioacetate 作用下， 生成 meso-2,4-pentanedithiol
  参考文献：
  名称：

  Phosphorus-containing cyclohexanes. Nuclear magnetic resonance studies and conformational analysis of 1,3,2-dithiaphosphorinanes

  摘要：

  DOI：

  10.1021/ja00405a025

文献信息

• Catalytic thioether and thioacetal formation using bis(diphenylphosphino)methane complexes of platinum (II)
  作者：Philip C. Bulman Page、Sukhbinder S. Klair、Michael P. Brown、Christopher S. Smith、Stephen J. Maginn、Suzanne Mulley

  DOI：10.1016/s0040-4020(01)90183-8

  日期：1992.7

  Bis(diphenylphosphino)methane complexes of platinum (II) catalyze the formation of thioethers from thiols and alkyl halides and of thioacetals from thiols or dithiols and geminal dihalides.

  铂（II）的双（二苯基膦基）甲烷络合物催化由硫醇和烷基卤化物形成硫醚，由硫醇或二硫醇和双晶二卤化物催化形成硫缩醛。
• Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates:  Synthesis, Reactivity, and Mechanism
  作者：Ming Li、Arkady Ellern、James H. Espenson

  DOI：10.1021/ja0519334

  日期：2005.7.1

  A series of rhenium(V) complexes, [(X)(ReO)(dt)(PPh(3))] and [(o-SC(6)H(4)PPh(2))(ReO)(mtp)], were prepared to explore electronic effects on the C-S cleavage reaction that occurs upon reaction with PAr(3) at ambient temperature [where X = S(C(6)H(4)-p-Z) (Z = OMe, Me, H, F, Cl), OPh, Cl, and SC(2)H(5), and dt is the chelating dithiolate ligand derived from 2-(mercaptomethyl)thiophenol, 1,2-ethanedithiol

  一系列铼(V)配合物，[(X)(ReO)(dt)(PPh(3))]和[(o-SC(6)H(4)PPh(2))(ReO)(mtp) ]，准备探索在环境温度下与 PAr(3) 反应时发生的 CS 裂解反应的电子效应 [其中 X = S(C(6)H(4)-pZ) (Z = OMe, Me, H 、F、Cl)、OPh、Cl 和 SC(2)H(5)，dt 是螯合二硫醇配体，衍生自 2-(巯基甲基)苯硫酚、1,2-乙二硫醇、1,3-丙二硫醇、1、 3-丁二硫醇和 2,4-戊二硫醇]。检查了 CS 激活的范围和选择性。CS 键裂解形成具有 ReS 核心的金属环 Re(V) 配合物仅发生在具有 mtp 和 pdt 框架和 X = SAr 和 SC(2)H(5) 的配合物。反应性的差异是由于辅助配体和二硫醇配体的供体能力不同，尤其是它们的供体能力，这在 CS 激活中起着关键作用。确定了 CS 活化过程的动力学；PPh(3)
• Carbon—sulphur bond formation catalysed by bis(diphenylphosphino)-methane complexes of platinum (II)
  作者：Philip C.Bulman Page、Sukhbinder S. Klair、Michael P. Brown、Marjorie M. Harding、Christopher S. Smith、Stephen J. Maginn、Suzanne Mulley

  DOI：10.1016/s0040-4039(00)80527-4

  日期：1988.1
• PAGE, PHILIP C. BULMAN;KLAIR, SUKHBINDER S.;BROWN, MICHAEL P.;HARDING, MA+, TETRAHEDRON LETT., 29,(1988) N 35, C. 4477-4480
  作者：PAGE, PHILIP C. BULMAN、KLAIR, SUKHBINDER S.、BROWN, MICHAEL P.、HARDING, MA+

  DOI：——

  日期：——
• Phosphorus-containing cyclohexanes. Nuclear magnetic resonance studies and conformational analysis of 1,3,2-dithiaphosphorinanes
  作者：Bruce E. Maryanoff、Andrew T. McPhail、Robert O. Hutchins

  DOI：10.1021/ja00405a025

  日期：1981.7