S-methyl 2-phenylethanethioate | 5925-74-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: S-methyl 2-phenylethanethioate
• 英文别名: methyl 2-phenyl ethanethionate；S-methyl phenylthioacetate；methyl 2-thiophenylacetate；methyl phenylthioacetate；S-Methyl phenylethanethioate
• CAS: 5925-74-6
• 化学式: C₉H₁₀OS
• 分子量: 166.244
• InChiKey: JZYDYNRKODRXIC-UHFFFAOYSA-N

物化性质

• 沸点：
  126 °C(Press: 11 Torr)
• 密度：
  0.9952 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 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 2-phenylethanethioate 在 4-二甲氨基吡啶 、 对甲苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 为溶剂， 反应 60.0h， 生成 S-methyl phenyldiazothioacetate
  参考文献：
  名称：

  Flash photolytic generation and reactivity of phenyl(methylthio)ketene in aqueous solution

  摘要：

  Methyl phenyldiazothioacetate is found to undergo Wolff rearrangement to phenyl(methylthio)ketene upon flash photolysis in aqueous solution and not to add water forming an ester enol as is the case with its oxygen analog, methyl phenyldiazoacetate. Hydration of phenyl(methylthio)ketene to alpha-(methylthio)phenylacetic acid occurs by both uncatalyzed and hydroxide ion catalyzed processes, whose rate constants, when compared to those for phenylketene, show the methylthio group to be rate-retarding. This is different from the effect of a hydroxyl group in the same position, which previous work had shown to be rate accelerating; possible reasons for this difference are advanced.

  DOI：

  10.1021/jo00050a019
• 作为产物：
  描述：

  4-(1-methylsulfanyl-2-phenyl-vinyl)-morpholine 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 S-methyl 2-phenylethanethioate
  参考文献：
  名称：

  Horner-Wittig方法制备S，N-烯酮缩醛：酸催化将S，N-烯酮缩醛水解为（S）-硫酯

  摘要：

  描述了甲酰基二苯基膦氧化物2的S，N-缩醛的合成。这些缩醛的稳定锂化阴离子与几种结构类型的醛一起用于Horner-Wittig反应中。以优异的产率获得了所得的S，N-烯酮缩醛1。酮和四乙醛不会与空间受阻的氧化膦阴离子反应。发现S，N-乙烯酮缩醛1在中等酸性条件下被选择性水解为相应的（S）-硫酯5。S的先前未描述的反应性，Ñ -ketene缩醛1所允许的醛的两步转化成同源的（小号）-thioesters 5以良好的收率。

  DOI：

  10.1016/0040-4020(96)00626-6

文献信息

• 4-Amino-1,5-dihydro-2<i>H</i>-pyrrol-2-one aus Bortrifluorid-katalysierten Umsetzungen von 3-Amino-2<i>H</i>-azirinen mit Carbonsäure-Derivaten
  作者：Martin Hugener、Heinz Heimgartner

  DOI：10.1002/hlca.19950780608

  日期：1995.9.20

  4-Amino-1,5-dihydro-2H-pyrrol-2-ones from Boron Trifluoride Catalyzed Reactions of 3-Amino-2H-azirines with Carboxylic Acid Derivatives

  三氟化硼的4-氨基-1,5-二氢-2 H-吡咯-2-酮催化3-氨基-2 H-叠氮基与羧酸衍生物的反应
• S,S-Dimethyl dithiocarbonate: A novel carbonyl dication synthon in the synthesis of ketones
  作者：Chiar-Dy Chen、Jui-Wen Huang、Man-kit Leung、Huei-hsu Li

  DOI：10.1016/s0040-4020(98)00544-4

  日期：1998.7

  We report herein the use of DMDTC as an effective carbonyl dication equivalent in ketone synthesis. According to our strategy, we also successfully devised a synthetic pathway for S-methyl (trimethylsilyl)thioacetate which may be a potentially useful synthetic reagent in organic synthesis.

  我们在此报道了DMDTC在酮合成中作为有效的羰基取代等价物的用途。根据我们的策略，我们还成功设计了S-甲基（三甲基甲硅烷基）硫代乙酸酯的合成途径，该途径可能是有机合成中潜在有用的合成试剂。
• Photochemical incorporation of protic solvents by open chain olefins
  作者：N. Miyamoto、H. Nozaki

  DOI：10.1016/0040-4020(73)80201-7

  日期：1973.1

  Irradition of methyl styryl sulphoxide dissolved in MeOH, EtOH, or AcOH induces the photochemical polar addition of the solvents to afford the product, PhCH(OR)CH2SOMe, where R is Me, Et, or Ac. By-products are the corresponding sulphides, PhCH(OR)CH2SMe, and methyl styryl sulphide. Similar adducts of protic solvents are produced upon irradiation of certain vinylic sulphides, methyl phenethynyl sulphide

  辐照溶解在MeOH，EtOH或AcOH中的甲基苯乙烯基亚砜会诱导溶剂的光化学极性加成，从而提供产物PhCH（OR）CH 2 SOMe，其中R为Me，Et或Ac。副产物是相应的硫化物，PhCH（OR）CH 2 SMe和甲基苯乙烯基硫化物。质子溶剂的类似加合物在某些乙烯基硫化物的辐照产生，甲基苯乙炔基硫化物，为包括以及适当取代propenylbenzenes ö -anethole，ø -anol和ö -propenylaniline在SOLN。
• Identification and biosynthesis of tropone derivatives and sulfur volatiles produced by bacteria of the marine Roseobacter clade
  作者：Verena Thiel、Thorsten Brinkhoff、Jeroen S. Dickschat、Susanne Wickel、Jörg Grunenberg、Irene Wagner-Döbler、Meinhard Simon、Stefan Schulz

  DOI：10.1039/b909133e

  日期：——

  Bacteria of the Roseobacter clade are abundant marine bacteria and are important contributors to the global sulfur cycle. The volatiles produced by two of its members, Phaeobacter gallaeciensis and Oceanibulbus indolifex, were analyzed to investigate whether the released compounds are derived from sulfur metabolism, and which biosynthetic pathways are involved in their formation. Both bacteria emitted different sulfides and thioesters, including new natural compounds such as S-methyl phenylethanethioate (16) and butyl methanesulfonate (21). The S-methyl alkanoates were identified by comparison with standards that were synthesized from the respective methyl alkanoates by a new method using an easily prepared aluminium/sulfur reagent. Phaeobacter gallaeciensis is also able to produce tropone (37) in large amounts. Its biosynthesis was investigated by various feeding experiments, showing that 37 is formed via a deviation of the phenylacetate catabolism. The unstable tropone hydrate 42 was identified as an intermediate of the tropone biosynthesis that was also released together with tropolone (38).

  Roseobacter 支系的细菌是丰富的海洋细菌，是全球硫循环的重要贡献者。研究人员分析了其中两个成员 Phaeobacter gallaeciensis 和 Oceanibulbus indolifex 产生的挥发性物质，以研究释放的化合物是否来自硫代谢，以及形成这些化合物的生物合成途径。两种细菌都释放出不同的硫化物和硫代酯，包括新的天然化合物，如 S-甲基苯硫酸盐（16）和甲基磺酸丁酯（21）。这些 S-甲基烷酸酯是通过与标准品进行比较而鉴定出来的，标准品是通过使用一种易于制备的铝/硫试剂的新方法从相应的甲基烷酸酯中合成的。加拉埃希氏芽孢杆菌也能大量生产托品酮（37）。通过各种喂养实验对其生物合成进行了研究，结果表明 37 是通过苯乙酸分解代谢的偏差形成的。不稳定的托品酮水合物 42 被确定为托品酮生物合成的中间产物，它也会与托品酮一起释放出来（38）。
• Acid-catalyzed hydrolysis of a phenylketene dithioacetal. Reversible protonation of the carbon-carbon double bond
  作者：Tadashi Okuyama、Takayuki Fueno

  DOI：10.1021/ja00351a044

  日期：1983.6

  Reactions of 1,1-bis(methylthio)-2-phenylethene(1) were followed in acidic CD/sub 3/CN-D/sub 2/O (50-90 vol %) solutions by /sup 1/H NMR spectroscopy. The H-D isotope exchange at the 2-position (to give 2-deuterio derivative 1-d) occurs concurrently with hydrolysis, which gives S-methyl phenylthioacetate. Relative rates of the isotope exchange to the hydrolysis increase from 1.0 to 13.4 on going from

  1,1-双(甲硫基)-2-苯基乙烯(1)在酸性CD/sub 3/CN-D/sub 2/O (50-90 vol %)溶液中的反应通过/sup 1/H NMR光谱进行跟踪. 2-位的 HD 同位素交换（得到 2-氘代衍生物 1-d）与水解同时发生，水解得到 S-甲基苯基硫代乙酸盐。随着 CD/sub 3/CN 含量从 50 vol% 增加到 90 vol%，同位素交换与水解的相对速率从 1.0 增加到 13.4。水解速率也通过紫外光谱法在 30/sup 0/C 下在 10 vol% CH/sub 3/CN-H/sub 2/O (D/sub 2/O) 中测量。1 在 CH/sub 3/CN-D/sub 2/O 中反应的伪一级曲线如同时同位素交换所预期的那样弯曲，在该介质中水解的相对交换速率为 2.1。氘代底物 1-d 的反应性约为 1 的 1.4 倍；这种明显的次级动力学同位素效应主要归因于 1-d