[2-(phenylsulfanyl)ethyl]benzene | 13865-49-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [2-(phenylsulfanyl)ethyl]benzene
• 英文别名: phenethyl(phenyl)sulfane；phenethyl phenyl sulfide；2-phenylethyl phenyl sulfide；Sulfide, phenethyl phenyl；2-phenylethylsulfanylbenzene
• CAS: 13865-49-1
• 化学式: C₁₄H₁₄S
• mdl: MFCD00020665
• 分子量: 214.331
• InChiKey: VRWWJIACGVONTQ-UHFFFAOYSA-N

物化性质

• 沸点：
  163-164 °C(Press: 15 Torr)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)
• LogP：
  4.439 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [2-(phenylsulfanyl)ethyl]benzene 在 manganese(IV) oxide 、 乙酰氯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以66%的产率得到(E)-[2-(phenylsulfanyl)vinyl]benzene
  参考文献：
  名称：

  Bellesia, Franco; Ghelfi, Franco; Pagnoni, Ugo Maria, Gazzetta Chimica Italiana, 1993, vol. 123, # 5, p. 289 - 291

  摘要：

  DOI：
• 作为产物：
  描述：

  phosphoric acid diethyl ester-(1-phenyl-vinyl ester) 在 三乙基硅烷 、 水 、 氧气 、 三氟乙酸 作用下， 反应 6.0h， 生成 [2-(phenylsulfanyl)ethyl]benzene
  参考文献：
  名称：

  水中活化烯烃的无催化剂双官能化：β-酮基硫化物和砜的高效合成

  摘要：

  直接合成一系列β-酮硫醚和β-酮砜的化学合成中，有效的策略是活化烯烃的双官能团化。由O 2介导的转化在水中顺利进行且没有任何催化剂。该方法的显着优势包括温和的反应条件，纯化简便和克级合成，这突显了该方法的实际实用性。

  DOI：

  10.1002/chem.201603041

文献信息

• Investigations on Gold‐Catalyzed Thioalkyne Activation Toward Facile Synthesis of Ketene Dithioacetals
  作者：Xiaohan Ye、Jin Wang、Shengtao Ding、Seyedmorteza Hosseyni、Lukasz Wojtas、Novruz G. Akhmedov、Xiaodong Shi

  DOI：10.1002/chem.201702710

  日期：2017.8.4

  from a gold‐associated thioketene intermediate. Based on this interesting mechanistic insight, a gold(I)‐catalyzed thioether addition to thioalkynes was developed as a novel approach to prepare ketene dithioacetals with good yields and high efficiency.

  在各种催化条件下研究了硫代炔烃的亲核加成反应，并确定金（I）配合物是最佳催化剂。产品的结构评估揭示了意外的顺式加成，由金缔合的硫烯酮中间体产生。基于这一有趣的机制见解，金（I）催化的硫醚加成硫代炔被开发为一种制备烯酮二硫缩醛的新方法，具有良好的收率和高效率。
• 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。
• Sulfamic acid: An efficient and recyclable catalyst for the regioselective hydrothiolation of terminal alkenes and alkynes with thiols
  作者：Clarissa Helena Rosa、Maura Luise B. Peixoto、Gilber Ricardo Rosa、Benhur Godoi、Fábio Zazyki Galetto、Marcelo Gonçalves Montes D'Oca、Marcelo Godoi

  DOI：10.1016/j.tetlet.2017.08.051

  日期：2017.9

  Herein, we described a new method for the preparation of thioethers through hydrothiolation of alkenes and alkynes, using sulfamic acid as a reusable catalyst. Generally, this new methodology afforded the desired products in very good yields, under metal and solvent-free conditions. Furthermore, the catalyst was easily recovered and reused for further catalytic reactions without loss of activity.

  在这里，我们描述了一种新的方法，该方法通过使用氨基磺酸作为可重复使用的催化剂，通过烯烃和炔烃的氢硫醇化来制备硫醚。通常，这种新方法可以在无金属和无溶剂的条件下以非常高的收率提供所需的产品。此外，该催化剂易于回收并重新用于进一步的催化反应而不会损失活性。
• Visible-light-activated selective synthesis of sulfoxides via thiol-ene/oxidation reaction cascade
  作者：Manjula Singh、Arvind K. Yadav、Lal Dhar S. Yadav、R.K.P. Singh

  DOI：10.1016/j.tetlet.2017.12.066

  日期：2018.1

  A convenient, highly selective and metal-free synthesis of sulfoxides from alkenes and thiols using NHPI as an inexpensive and reusable organophotoredox catalyst is reported. The protocol involves radical thiol-ene/oxidation reaction cascade and utilizes visible light and air (O2) as inexpensive, readily available, non-toxic and eco-sustainable reagents to afford up to 96% yields of the product at

  据报道，使用NHPI作为廉价且可重复使用的有机光氧化还原催化剂，可从烯烃和硫醇方便，高度选择性且无金属地合成亚砜。该方案涉及自由基硫醇-烯/氧化反应级联，并利用可见光和空气（O 2）作为廉价，易于获得，无毒且生态可持续的试剂，在室温下提供高达96％的产物收率。
• Acid-Catalyzed Oxidative Addition of Thiols to Olefins and Alkynes for a One-Pot Entry to Sulfoxides
  作者：Martin Klussmann、Hui-Lan Yue

  DOI：10.1055/s-0035-1562480

  日期：——

  An oxidative variant of the thiol-ene reaction has been developed, achieving the direct addition of thiols to olefins to form sulfoxides. The reaction uses tert-butyl hydroperoxide as oxidant and methanesulfonic acid as catalyst. The latter is believed to catalyze the oxidation of the intermediate sulfide to the sulfoxide. No special precautions are necessary to exclude oxygen, yet the products are

  已开发出硫醇-烯反应的氧化变体，实现了硫醇与烯烃的直接加成以形成亚砜。该反应以叔丁基过氧化氢为氧化剂，甲磺酸为催化剂。据信后者催化中间体硫化物氧化成亚砜。不需要特殊的预防措施来排除氧气，但产物在 β 位没有氧化的情况下形成。苯乙烯、丙烯酸衍生物、炔烃和苯硫酚的产率最高，而脂肪族烯烃和硫醇的效果较差。

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