ethyl bis(methylthio)acetate | 7023-83-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: ethyl bis(methylthio)acetate
• 英文别名: ethyl bis(methylsulfanyl)acetate；Dimethylmercaptoessigsaeure-aethylester；bis-methylsulfanyl-acetic acid ethyl ester；Bis-methylmercapto-essigsaeure-aethylester；ethyl 2,2-bis(methylsulfanyl)acetate
• CAS: 7023-83-8
• 化学式: C₆H₁₂O₂S₂
• 分子量: 180.292
• InChiKey: QHXKFJMNMUICNS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl bis(methylthio)acetate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以83%的产率得到2,2-bis-methylsulfanyl-ethanol
  参考文献：
  名称：

  A new synthetic entry to pentacyclic Strychnos alkaloids. Total synthesis of (.+-.)-tubifolidine, (.+-.)-tubifoline, and (.+-.)-19,20-dihydroakuammicine

  摘要：

  A new strategy for the synthesis of pentacyclic Strychnos alkaloids has been developed. It consists in the closure of the five-membered E ring by cyclization upon the indole 3-position from a suitably N-substituted tetracyclic system embodying rings ABCD of the alkaloids. Attempts to effect the key cyclization either by Pummerer rearrangement of sulfinylacetamides 4 and 6, from chloroacetamide 12, or from bis(methylthio)acetamide 10b (exocyclic amide carbonyl group) resulted in failure. In the first case dithioacetals 9 and 10, respectively, were formed in good yields. Cyclization from alcohol 13 or from the indole-deactivated acetal 15 and dithiocetal 18 were also unsuccessful: noncyclized products coming from the initially formed oxonium or thionium intermediates 16 were obtained. Cyclization was satisfactorily accomplished in 49% yield by treatment of the N-unsubstituted indole dithioacetal 23 with DMTSF. The resulting pentacycle 25 was converted to 20-deethyltubifolidine (27). A similar treatment from dithioacetal 41a, prepared from the secondary amine 32a, afforded pentacycle 42a, from which the alkaloids tubifoline, tubifolidine, and 19,20-dihydroakuammicine were synthesized.

  DOI：

  10.1021/jo00313a017
• 作为产物：
  描述：

  甲基硫代磺酸甲酯 、 丙二酸单乙酯 在 sodium hydride 作用下， 以 二甲基亚砜 、 paraffin 为溶剂， 反应 4.5h， 以64%的产率得到ethyl bis(methylthio)acetate
  参考文献：
  名称：

  Wladislaw, Blanka; Marzorati, Liliana; Donnici, Claudio L., Journal of the Chemical Society. Perkin transactions I, 1993, # 24, p. 3167 - 3170

  摘要：

  DOI：

文献信息

• On the thermal Pummerer rearrangement of substituted sulfoxides
  作者：Liliana Marzorati、Eduardo K.C. Yoshikawa、Ataualpa A.C. Braga、Claudio Di Vitta

  DOI：10.1080/17415993.2013.853066

  日期：2014.5.4

  Sulfoxides bearing thioester and ester groups at the α position under heating at ca. 140°C undergo Pummerer thermal rearrangement. However, for sulfonyl sulfoxide, a complex mixture of products is formed. Plausible mechanism is advanced. GRAPHICAL ABSTRACT

  在 α 位带有硫酯和酯基团的亚砜在约 10 ℃加热。140°C进行Pummerer热重排。然而，对于磺酰亚砜，会形成复杂的产物混合物。合理的机制是先进的。图形概要
• Electrophilic aromatic substitution by pummerer reaction of α-sulfinylacetate
  作者：Y. Tamura、H.-D. Choi、H. Shindo、J. Uenishi、H. Ishibashi

  DOI：10.1016/0040-4039(81)80046-9

  日期：1981.1

  Treatment of a mixture of aromatic compound and ethyl α-(methylsulfinyl)acetate (5) with p-toluenesulfonic acid under continuous removal of separated water brought about an intermolecular aromatic substitution to give ethyl α-(methylthio)arylacetate (6). Similar treatment of acylmethyl phenethyl sulfoxide (8) led to cyclization into 1-acylisothiochroman (9).

  在连续除去分离的水的情况下，用对甲苯磺酸处理芳族化合物和α-（甲基亚磺酰基）乙酸乙酯（5）的混合物，引起分子间的芳族取代，得到α-（甲基硫代）芳基乙酸乙酯（6）。对酰基甲基苯乙基亚砜（8）的类似处理导致环化成1-酰基异硫代苯并二氢吡喃（9）。
• Boehme; Huang, Archiv der Pharmazie, 1944, p. 15
  作者：Boehme、Huang

  DOI：——

  日期：——
• AMAT, MERCEDES;LINARES, ANA;BOSCH, JOAN, J. ORG. CHEM., 55,(1990) N6, C. 6299-6312
  作者：AMAT, MERCEDES、LINARES, ANA、BOSCH, JOAN

  DOI：——

  日期：——
• TAMURA Y.; CHOI H.-D.; SHINDO H.; UENISHI J.; ISHIBASHI H., TETRAHEDRON LETTERS, 1981, 22, 81-84
  作者：TAMURA Y.、 CHOI H.-D.、 SHINDO H.、 UENISHI J.、 ISHIBASHI H.

  DOI：——

  日期：——