S-methyl α-chlorothioacetate | 5925-71-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硫代羧酸及其衍生物
• 英文名称: S-methyl α-chlorothioacetate
• 英文别名: S-methyl chlorothioacetate；chloro-thioacetic acid S-methyl ester；Chlor-thioessigsaeure-S-methylester；S-methyl alpha-chlorothioacetate；S-methyl 2-chloroethanethioate
• CAS: 5925-71-3
• 化学式: C₃H₅ClOS
• 分子量: 124.591
• InChiKey: QASUKTWOCVXMIO-UHFFFAOYSA-N

物化性质

• 沸点：
  160 °C
• 密度：
  1.239±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  S-methyl α-chlorothioacetate 以54%的产率得到Trithiooxalsaeure-S,S-dimethylester
  参考文献：
  名称：

  Guenther, Horst; Voss, Juergen, Journal of Chemical Research, Miniprint, 1987, # 3, p. 775 - 789

  摘要：

  DOI：
• 作为产物：
  描述：

  2-Chloro-thioacetimidic acid methyl ester; hydrochloride 在 水 作用下， 生成 S-methyl α-chlorothioacetate
  参考文献：
  名称：

  Mayer,R. et al., Chemische Berichte, 1966, vol. 99, p. 1393 - 1413

  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
• A comparison of reactivity of (EtO)2P(O)CH2I with related non-phosphorus-containing iodides in the radical iodine atom transfer addition
  作者：Piotr Ba?czewski、Tomasz Bia?as、Aldona Szadowiak

  DOI：10.1002/hc.10121

  日期：——

  Based on competitive reactions and 1H NMR measurements, it was found that (EtO)2P(O)CH2I is at least 2–3 orders of magnitude less reactive than other non-phosphorus iodides of the EWG-CH2I type (EWG = NC, COOMe, 4-Br-C6H4CO). MeSCH2I turned out to be totally unreactive in the title reaction. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:186–188, 2003; Published online in Wiley InterScience (www

  基于竞争反应和 1H NMR 测量，发现 (EtO)2P(O)CH2I 的反应性比 EWG-CH2I 类型的其他非磷碘化物（EWG = NC，COOMe）低至少 2-3 个数量级, 4-Br-C6H4CO)。MeSCH2I 在标题反应中完全没有反应。© 2003 Wiley Periodicals, Inc. 杂原子化学 14:186–188, 2003; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.10121
• Conformational behaviour in <i>S-</i>methyl halothioacetates through NMR, FT-IR, and theoretical calculations
  作者：Ernani A Basso、Barbara C Fiorin、Cláudio F Tormena、Roberto Rittner

  DOI：10.1139/v03-189

  日期：2004.3.1

  This work presents an investigation of the conformational behaviour of S-methyl chlorothioacetate (MCTA), S-methyl bromothioacetate (MBTA), and S-methyl iodothioacetate (MITA) through NMR and IR spectroscopies and through theoretical calculations that apply DFT/B3LYP theory. The DFT calculations showed two stable rotamers in the vapour phase, gauche and trans, for all the compounds. The coupling constants, ¹J_CH, were obtained from NMR spectroscopy; these were used in the solvation theory to calculate the vapour-phase energy difference, the coupling constants for each rotamer, the solution energy difference, and the rotamer population for each solvent. These data showed that for MCTA, the most stable rotamer is trans; however, for MBTA and MITA, the most stable rotamer is gauche, both in the vapour phase and in solution. The changes in rotamer stability are because of the preference in stereo-electronic interactions; in the MCTA case the interaction is mainly electrostatic, while for MBTA and MITA, it is because of the interaction between n_Br,I[Formula: see text]π^*_CO.Key words: S-methyl halothioacetates, conformational analysis, theoretical calculations, NMR, solvation theory.

  这项工作通过NMR和IR光谱以及应用DFT/B3LYP理论的理论计算，对S-甲基氯硫代酸酯（MCTA）、S-甲基溴硫代酸酯（MBTA）和S-甲基碘硫代酸酯（MITA）的构象行为进行了研究。DFT计算显示，在气相中，所有化合物都有两种稳定的旋转异构体： gauche和trans。通过NMR光谱获得偶合常数¹J_CH，并在溶剂化理论中使用这些常数，计算了气相能量差异、每个旋转异构体的偶合常数、溶液能量差异和每个溶剂的旋转异构体的比例。这些数据表明，对于MCTA，最稳定的旋转异构体是trans；然而，对于MBTA和MITA，最稳定的旋转异构体是gauche，无论是在气相中还是在溶液中。旋转异构体稳定性的变化是由于立体电子相互作用的偏好；在MCTA的情况下，相互作用主要是静电作用，而对于MBTA和MITA，则是由于n_Br,I[Formula: see text]π^*_CO之间的相互作用。关键词：S-甲基卤硫代酸酯，构象分析，理论计算，NMR，溶剂化理论。
• Hydrolysis of acyl-activated thiol esters. Acid catalysis and acid inhibition
  作者：Robert. Hershfield、Gaston L. Schmir

  DOI：10.1021/ja00793a027

  日期：1973.6
• Arndt; Bekir, Chemische Berichte, 1930, vol. 63, p. 2393,2396
  作者：Arndt、Bekir

  DOI：——

  日期：——