Tris-(methylmercapto)-acetaldehyd | 21247-24-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Tris-(methylmercapto)-acetaldehyd
• 英文别名: 2,2,2-Tris(methylsulfanyl)acetaldehyde
• CAS: 21247-24-5
• 化学式: C₅H₁₀OS₃
• 分子量: 182.332
• InChiKey: NRDGQQXNNNLAKW-UHFFFAOYSA-N

物化性质

• 沸点：
  74-75 °C(Press: 0.5 Torr)
• 密度：
  1.212±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  93
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Tris-(methylmercapto)-acetaldehyd 在 tetrafluoroboric acid 、 potassium iodide 、 mercury(II) oxide 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以61%的产率得到S-methyl thioglyoxylate
  参考文献：
  名称：

  A Simple and High Yield General Route to Methyl α-Oxo Thiolcarboxylates

  摘要：

  甲基-β-氧代硫羧酸酯（脂肪族、芳香族和杂芳族）可通过在THF水溶液中用N-溴代琥珀酰亚胺或用HgO/35% HBF4水溶液水解相应的三甲基-β-氧代三硫代邻酯，获得良好至极佳的收率。

  DOI：

  10.1055/s-1996-4234
• 作为产物：
  描述：

  三(甲基硫代)甲烷 、 甲酸甲酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以93%的产率得到Tris-(methylmercapto)-acetaldehyd
  参考文献：
  名称：

  Synthesis of trimethyl .alpha.-keto trithioorthoesters and dimethyl .alpha.-keto dithioacetals by reaction of esters with tris(methylthio)methyllithium

  摘要：

  A complete study has been made of the reaction of tris(methylthio)methyllithium with aromatic, heteroaromatic, and aliphatic esters. It is a one-pot reaction that despite its complexity, and depending on the reagent ratios, the reaction conditions, and the possible use of additional reagents (N-(methylthio)phthalimide or BuLi), can supply easily, in excellent and reproducible yields, the trimethyl alpha-keto trithioorthoesters 3 or, alternatively, the dimethyl a-keto dithioacetals 4. The reaction mechanism has been elucidated.

  DOI：

  10.1021/jo00124a009

文献信息

• Reactions of Group IV organometallic compounds. Part XI. Some insertion reactions of alkylsilyl and alkylstannyl sulphides
  作者：Kenji Itoh、Kimishige Matsuzaki、Yoshio Ishii

  DOI：10.1039/j39680002709

  日期：——

  Reaction of trimethylsilyl sulphide with phenyl isocyanate gives a 1 : 1 insertion product, but subsequent insertion of phenyl isocyanate takes place readily in the case of trialkylstannyl sulphide, to produce triphenyl isocyanurate. When chloral is used as a reactant for trialkyltin sulphides, substitution of all three chlorine atoms occurs, to afford trialkyltin chloride and (RS)3C·CHO, although

  三甲基甲硅烷基硫醚与异氰酸苯酯的反应生成1：1的插入产物，但是在三烷基锡烷基硫醚的情况下，异氰酸苯酯的随后插入很容易发生，从而生成异氰脲酸三苯酯。当将氯醛用作三烷基锡硫化物的反应物时，尽管在三烷基甲硅烷基硫化物的情况下获得了简单的插入产物，但所有三个氯原子都被取代，从而得到三烷基氯化锡和（RS）3 C·CHO。β-丙内酯的烷基-氧键裂解已选择性地与Si-S化合物反应。
• Isomerization of Trimethyl α-Keto Trithioorthocarboxylates into α,α-Bis(methylthio) Thiolcarboxylates. A New Rearrangement of Synthetic Interest
  作者：Iacopo Degani、Stefano Dughera、Rita Fochi、Sonia Gazzetto

  DOI：10.1021/jo970683+

  日期：1997.10.1

  A study was made of the isomerization reaction of a great variety of trimethyl alpha-keto trithioorthocarboxylates to alpha,alpha-bis(methylthio) thiolcarboxylates, intermediates of high synthetic value for the synthesis of alpha-arylpropionic acids. The reaction was carried out In methylene chloride in the presence of catalytic amounts of trityl perchlorate or methanesulfonic acid and was complete in 2 h at rt. In most of the investigated cases the result was positive, the yields usually being greater than 90%. Also the reaction mechanism was subjected to an experimental study.
• Synthesis of Trimethyl α-Keto Trithioorthoesters and Dimethyl α-Keto Dithioacetals by Reaction of Acyl Chlorides, Anhydrides, Thiol Esters, and <i>N</i>,<i>N</i>-Dimethylamides with [Tris(methylthio)methyl]lithium
  作者：Iacopo Degani、Stefano Dughera、Rita Fochi、Emanuela Serra

  DOI：10.1021/jo961194x

  日期：1996.1.1
• Synthesis of trimethyl .alpha.-keto trithioorthoesters and dimethyl .alpha.-keto dithioacetals by reaction of esters with tris(methylthio)methyllithium
  作者：Margherita Barbero、SIlvano Cadamuro、Iacopo Degani、Stefano Dughera、Rita Fochi

  DOI：10.1021/jo00124a009

  日期：1995.9

  A complete study has been made of the reaction of tris(methylthio)methyllithium with aromatic, heteroaromatic, and aliphatic esters. It is a one-pot reaction that despite its complexity, and depending on the reagent ratios, the reaction conditions, and the possible use of additional reagents (N-(methylthio)phthalimide or BuLi), can supply easily, in excellent and reproducible yields, the trimethyl alpha-keto trithioorthoesters 3 or, alternatively, the dimethyl a-keto dithioacetals 4. The reaction mechanism has been elucidated.
• A Simple and High Yield General Route to Methyl α-Oxo Thiolcarboxylates
  作者：Iacopo Degani、Stefano Dughera、Rita Fochi、Antonella Gatti

  DOI：10.1055/s-1996-4234

  日期：1996.4

  Methyl α-oxo thiolcarboxylates (aliphatic, aromatic and heteroaromatic) are obtained in good to excellent yields by hydrolysis of the corresponding trimethyl α-oxo trithioorthoesters with N-bromosuccinimide in aqueous THF or with HgO/35% aqueous HBF4 ves.

  甲基-β-氧代硫羧酸酯（脂肪族、芳香族和杂芳族）可通过在THF水溶液中用N-溴代琥珀酰亚胺或用HgO/35% HBF4水溶液水解相应的三甲基-β-氧代三硫代邻酯，获得良好至极佳的收率。