tetrathioorthocarbonic acid tetramethyl ester | 6156-25-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: tetrathioorthocarbonic acid tetramethyl ester
• 英文别名: tetramethyl-orthothiocarbonate；Tetrakis-methylmercapto-methan；Tetrathioorthokohlensaeure-tetramethylester；Methane, tetrakis(methylthio)-；tetrakis(methylsulfanyl)methane
• CAS: 6156-25-8
• 化学式: C₅H₁₂S₄
• 分子量: 200.414
• InChiKey: VIKWCIAIVDLETK-UHFFFAOYSA-N

物化性质

• 熔点：
  65.55°C
• 沸点：
  298.17°C (rough estimate)
• 密度：
  1.181 (estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrathioorthocarbonic acid tetramethyl ester 在 monoperoxyphthalic acid 作用下， 生成 tris-methanesulfonyl-methane
  参考文献：
  名称：

  Backer, Recueil des Travaux Chimiques des Pays-Bas, 1946, vol. 65, p. 54

  摘要：

  DOI：
• 作为产物：
  描述：

  S-甲基异硫脲硫酸盐 在 盐酸 、 乙醚 、 sodium nitrite 作用下， 生成 tetrathioorthocarbonic acid tetramethyl ester
  参考文献：
  名称：

  Backer; Stedehouder, Recueil des Travaux Chimiques des Pays-Bas, 1933, vol. 52, p. 930

  摘要：

  DOI：

文献信息

• Synthetic Application of Tris(methylthio)methyl Salts. An Efficient Route to Trithioorthocarboxylic Esters from Strongly Activated Aromatic and Heteroaromatic Systems
  作者：Margherita Barbero、Silvano Cadamuro、Iacopo Degani、Rita Fochi、Antonella Gatti、Valeria Regondi

  DOI：10.1055/s-1988-27455

  日期：——

  Nine trithioorthocarboxylic esters were synthesized by reaction of tris(methylthio)methyl methyl sulfate or tetrafluoroborate with electron-rich aromatic and heteroaromatic compounds, i.e. N,N-dialkylarylamines, pyrroles, and indoles. The new procedure is simple and offers the following advantages: easy preparation of reagents; mild reaction conditions; possibility to introduce two tris(methylthio)methyl groups into the same ring, good to excellent yields.

  通过三(甲硫基)甲基硫酸盐或四氟硼酸盐与富含电子的芳香族和杂芳香族化合物（即 N,N-二烷基芳胺、吡咯和吲哚）反应，合成了九种三硫代正羧酸酯。新方法简单易行，具有以下优点：试剂易于制备；反应条件温和；可在同一环中引入两个三（甲硫基）甲基；收率高至极佳。
• A convenient new route to enantiopure 3-hydroxy-5-oxo esters and 5,6-dihydropyran-2-ones: intricacies of the trithioorthoester protecting group
  作者：Rebecca L. Grange、Craig M. Williams

  DOI：10.1016/j.tetlet.2009.12.058

  日期：2010.2

  3-Hydroxy-5-oxo esters are useful precursors to biologically active compounds. An expedient three-step synthesis of 3-hydroxy-5-oxo esters based on dithiane anion chemistry is presented along with the transformation of the 3-hydroxy-5-oxo esters into 5,6-dihydropyran-2-ones.

  3-羟基-5-氧代酯是生物活性化合物的有用前体。提出了一种基于双硫醚阴离子化学方法的3-羟基-5-氧代酯的简便三步合成方法，以及将3-羟基-5-氧代酸酯转化为5,6-二氢吡喃-2-酮的方法。
• 1,3-intramolecular metal shifts in some pentacarbonyl-chromium and -tungsten derivatives of bis-, tris- and tetrakis(methylthio)methane and bis(methylseleno)methane. A dynamic nuclear magnetic resonance investigation
  作者：Edward W. Abel、Thomas E. Mackenzie、Keith G. Orrell、Vladimir Šik

  DOI：10.1016/s0277-5387(00)86551-1

  日期：1987.1

  synthesized and characterized. In addition to the facile atomic inversions of the metal co-ordinated sulphur and selenium atoms, there are intramolecular 1,3-metallotropic shifts among all the available co-ordination sites on each ligand. From dynamic NMR studies activation energies have been determined for these metal commutations.

  摘要单核络合物[M（CO）5（CH 3 E）n CH 4− n]（n = 2，M = Cr和W，E = S和Se; n = 3，M = Cr和W，E = S； n = 4，M = Cr，E = S）已经合成并表征。除了金属配位的硫和硒原子的易原子反转外，在每个配体上所有可用的配位位点之间还存在分子内的1,3-金属向位移。根据动态NMR研究，已经确定了这些金属换向的活化能。
• Synthetic Routes to 3,9-Dimethylidene-1,5,7,11-tetrathiaspiro[5.5]undecane
  作者：MK Bromley、SJ Gason、AG Jhingran、MG Looney、DH Solomon

  DOI：10.1071/ch9961261

  日期：——

  Spiro orthocarbonates ( SOCs ) have been widely studied, particularly as monomers which on polymerization undergo minimal shrinkage. Of particular interest has been the dimethylidene SOC because, unlike the parent SOC, it is amenable to free-radical polymerization. The incorporation of other hetero atoms, particularly sulfur, into the bicyclic structure offers the potential of polymers with improved refractive indices and mechanical properties. However, whilst literature methods are available for the spiro tetrathioorthocarbonates ( STOCs ),3 the synthesis of a methylidene derivative has not been reported. In this communication we report the synthesis of 3,9-dimethylidene-1,5,7,11-tetra-thiaspiro[5.5] undecane (DMSTOC) (1).

  Spiro正交碳酸酯（SOCs）已被广泛研究，特别是作为单体，在聚合过程中经历最小的收缩。特别值得关注的是二甲基亚碳酸酯，因为与原SOC不同，它易于自由基聚合。将其他杂原子，特别是硫，纳入到双环结构中，可以提供具有改进的折射率和机械性能的聚合物的潜力。然而，虽然文献中已经提供了Spiro四硫代正交碳酸酯（STOCs）的合成方法，但是甲基亚碳酸酯衍生物的合成尚未报道。在本文中，我们报告了3,9-二甲基亚碳酸酯-1,5,7,11-四硫代Spiro [5.5]十一烷（DMSTOC）（1）的合成。
• Heat capacity and phase transitions of the orientationally disordered crystal C(SCH3)4
  作者：Michio Sorai、Keisuke Kimura、Alarich Weiss、Roman Strauss

  DOI：10.1006/jcht.1998.0442

  日期：1998.12

  −1 ; transition from phase II to I, T trs =318.76 K, Δ trs H m =7.29 kJ · mol −1 , Δ trs S m =22.87 J · K −1 ·mol −1 ; transition from phase I to liquid, T fus =338.89 K, Δ fus H m =3.31 kJ · mol −1 , Δ fus S m =9.77 J · K −1 ·mol −1 . The highest temperature crystalline phase I can be assigned as an orientationally disordered state, which is established by two-step phase transitions. The entropy gains

  摘要 使用绝热量热计测定了温度T =（13至360）K下四(甲硫基)甲烷C(SCH 3 ) 4 的热容。观察到三个一级相变，其温度和焓和熵增益确定如下：从相 III 到 II 相的转变，T trs =296.23 K，Δ trs H m =7.09 kJ·mol -1 ，Δ trs S m =23.93 J·K -1 ·mol -1 ；从II相到I相的转变，T trs =318.76 K，Δ trs H m =7.29 kJ·mol -1 ，Δ trs S m =22.87 J·K -1 ·mol -1 ；从I相到液体的转变，T fus =338.89 K，Δ fus H m =3.31 kJ·mol -1 ，Δ fus S m =9.77 J·K -1 ·mol -1 。最高温度的结晶相 I 可以被指定为取向无序状态，这是通过两步相变建立的。固态中发生相变时的熵增益可以很好地解释为晶格中