dimethyl α-phenylthiomalonate | 37054-53-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: dimethyl α-phenylthiomalonate
• 英文别名: dimethyl 2-(phenylthio)malonate；dimethyl (phenylthio)malonate；dimethyl phenylthiomalonate；dimethylphenylthiomalonate；Phenylmercapto-malonsaeure-dimethylester；Phenyl-bis(carbomethoxy)methylsulfid；Dimethyl 2-phenylsulfanylpropanedioate
• CAS: 37054-53-8
• 化学式: C₁₁H₁₂O₄S
• 分子量: 240.28
• InChiKey: NBCNRBFLONCMPP-UHFFFAOYSA-N

物化性质

• 沸点：
  313.3±32.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  77.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl α-phenylthiomalonate 在 镍 四氯化钛 、 三乙胺 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  区域和立体选择性地将双（甲氧基羰基）甲基引入哌啶骨架的γ位

  摘要：

  探索了将双（甲氧基羰基）-甲基区域选择性地引入哌啶骨架的4-位的新方法，并将该方法用于制备从-开始的顺式和反式-2,4-二取代的哌啶2-哌啶羧酸。该方法的关键步骤涉及氨基甲酸酯的电化学氧化。

  DOI：

  10.1016/0040-4039(96)01208-7
• 作为产物：
  描述：

  苯硫酚 在 氧气 、 potassium iodide 、 sodium hydroxide 作用下， 以 乙腈 为溶剂， 80.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 生成 dimethyl α-phenylthiomalonate
  参考文献：
  名称：

  KI-catalyzed C–S bond formation via an oxidation relay strategy: efficient access to various α-thio-β-dicarbonyl compounds

  摘要：

  在碱性条件下，通过碘化钾（KI）催化，提出了一种获得α-硫代-β-二羰基化合物的高效实用方法。

  DOI：

  10.1039/c8ob00080h

文献信息

• Pyrolysis of (2-Phenylethyl)phenylsulfonium Ylides.
  作者：Toshiaki Yoshimura、Atsushi Motoyama、Akiko Morishige、Eiichi Tsukurimichi、Choichiro Shimasaki、Kiyoshi Hasegawa

  DOI：10.1246/bcsj.66.174

  日期：——

  In order to obtain information concerning the reaction mechanism of the pyrolysis of sulfonium ylides bearing a substituted phenyl group on the 2-position in the S-ethyl group of ethylphenylsulfonium ylide, (2-phenylethyl)phenylsulfonium bis(methoxycarbonyl)methylide (1) and dicyanomethylide (2) were subjected to pyrolysis in benzene. The reaction rates of 1 and 2 at 140 °C were 6.0- and 3.2-times faster than those of ethylphenylsulfonium bis(methoxycarbonyl)methylide and dicyanomethylide, respectively. The activation parameters for 1 were ΔH‡ = 125 kJ mol−1 and ΔS‡ = −3.8 J K−1 mol−1, while those for 2 were ΔH‡ = 124 kJ mol−1 and ΔS‡ = −2.5 J K−1 mol−1. Substituent effects on the β-phenyl groups in 1 and 2 afforded positive Hammett ρ-values: ρ = 0.49 (γ = 0.997) and ρ = 0.26 (γ = 0.993), respectively.From the obtained results, it was suggested that the pyrolysis proceeds through essentially a concerted intramolecular cis-elimination inclined toward a slightly carbanion-like type from an E1-like type by introducing a phenyl substituent at the 2-position of the ethyl group in the ethylphenylsulfonium ylide.

  为了获取有关乙基苯基亚磺酸乙酯中乙基的2-位上带有取代苯基的磺酸亚磺酸分解反应机理的信息，将（2-苯乙基）苯基亚磺酸双（甲氧基羰基）甲亚基（1）和双氰基甲亚基（2）在苯中进行分解。在140°C时，1和2的反应速率分别比乙基苯基亚磺酸双（甲氧基羰基）甲亚基和双氰基甲亚基快6.0倍和3.2倍。1的活化参数为ΔH‡ = 125 kJ mol−1，ΔS‡ = -3.8 J K−1 mol−1，而2的活化参数为ΔH‡ = 124 kJ mol−1，ΔS‡ = -2.5 J K−1 mol−1。1和2中β-苯基的取代效应提供了正的Hammett ρ值：ρ = 0.49（γ = 0.997）和ρ = 0.26（γ = 0.993）。从得到的结果可以看出，通过在乙基苯基亚磺酸乙的乙基的2-位引入苯基取代基，基本上是通过倾向于稍微类似于碳负离子的顺式消除过程，从而类似于E1型反应。
• Gold-Catalyzed Oxidation of Thioalkynes To Form Phenylthio Ketene Derivatives via a Noncarbene Route
  作者：Pankaj Sharma、Rahulkumar Rajmani Singh、Sovan Sundar Giri、Liang-Yu Chen、Mu-Jeng Cheng、Rai-Shung Liu

  DOI：10.1021/acs.orglett.9b01768

  日期：2019.7.19

  Gold-catalyzed oxidations of thioalkynes with 8-methylquinoline oxides afford 2-phenylthioketenes that can be trapped efficiently with alcohols. The synthetic utility is manifested by terminal and internal thioalkynes over a wide scope, bearing esters, ketones, alkyl, and oxime substituents. Our density functional theory calculations suggest that gold-catalyzed oxidations of terminal and internal thioalkynes

  金催化的8-甲基喹啉氧化物氧化硫代炔烃可生成2-苯基硫代烯酮，可被醇有效地捕集。末端和内部的硫代炔烃在广泛的范围内带有酯，酮，烷基和肟取代基，从而显示出合成的效用。我们的密度泛函理论计算表明，用8-甲基喹啉氧化物对末端和内部硫代炔烃进行金催化的氧化反应可生成与金键合的乙烯酮中间体，而无需使用α-氧代金卡宾。
• The reduction of semipolar linkages by O,O-dialkyl dithiophosphoric acid
  作者：S. Oae、A. Nakanishi、N. Tsujimoto

  DOI：10.1016/0040-4020(72)80012-7

  日期：1972.1

  Compounds having a semipolar functional group, generally formulated X → Y, i.e. sulfoxide, sulfilimine, sulfonium ylide, pyridine N-oxide, and N-iminopyridinium betaine, were found to react readily with O,O-dialkyl dithiophosphoric acid to afford the corresponding reduction products, sulfide and pyridine.

  发现具有半极性官能团的化合物（通常由X→Y表示），即亚砜，亚硫亚胺，鎓内鎓盐，吡啶N-氧化物和N-亚氨基吡啶甜菜碱，很容易与O，O-二烷基二硫代磷酸反应以提供相应的还原产品，硫化物和吡啶。
• σ‐Holes in Iodonium Ylides: Halogen‐Bond Activation of Carboxylic Acids, Phenols and Thiophenols May Enable Their X−H Insertion Reactions
  作者：Carlee A. Montgomery、Islam Jameel、Fabio Cuzzucoli、Tristan Chidley、W. Scott Hopkins、Graham K. Murphy

  DOI：10.1002/chem.202202029

  日期：2022.12.20

  iodonium ylides to possess two σ-holes of differing potentials, situated along the extensions of their C−I bonds. Experimentation revealed that formal O−H or S−H insertion reactions were possible with carboxylic acids, phenols and thiophenols. Halogen-bond activation is presumed to be essential, resulting in α-substituted-β-dicarbonyls in 64 %–99 % yield in five minutes.

  计算分析表明，碘鎓叶立德具有两个不同电位的 σ 孔，位于其 C−I 键的延伸线上。实验表明，正式的 O−H 或 S−H 插入反应可能与羧酸、酚类和苯硫酚有关。卤键活化被认为是必不可少的，导致 α-取代的-β-二羰基化合物在五分钟内以 64%–99% 的产率生成。
• Takeuchi, Yoshio; Makino, Yutaka; Maruyama, Koichi, Heterocycles, 1980, vol. 14, # 2, p. 163 - 168
  作者：Takeuchi, Yoshio、Makino, Yutaka、Maruyama, Koichi、Yoshii, Eiichi

  DOI：——

  日期：——