2-(烯丙基硫基)苯甲酰氯 | 158667-07-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-(烯丙基硫基)苯甲酰氯
• 英文名称: 2-(allylthio)benzoyl chloride
• 英文别名: 2-[(Prop-2-en-1-yl)sulfanyl]benzoyl chloride；2-prop-2-enylsulfanylbenzoyl chloride
• CAS: 158667-07-3
• 化学式: C₁₀H₉ClOS
• 分子量: 212.7
• InChiKey: JAWOOMCTNOHBHC-UHFFFAOYSA-N

物化性质

• 沸点：
  286.5±33.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  2-(烯丙基硫基)苯甲酰氯 在 sodium tetrahydroborate 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 3-methylenethiochroman-4-one
  参考文献：
  名称：

  Photoinduced Free Radical Chemistry of the Acyl Tellurides: Generation, Inter- and Intramolecular Trapping, and ESR Spectroscopic Identification of Acyl Radicals

  摘要：

  Acyl tellurides are prepared in good to excellent yield by the reaction of sodium aryl tellurides with acyl chlorides, or mixed anhydrides, and are found to be moderately air-stable substances. In contrast to previous literature reports, acyl tellurides of aryl and vinyl carboxylic acids are found to be excellent sources of acyl radicals on photolysis with a simple white light source. The acyl radicals so generated may be trapped intermolecularly by dichalcogenides, or by TEMPO in excellent yield. Trapping by N-tert-butyl-alpha-phenyl nitrone produces a stable nitroxide radical which has been characterized by ESR spectroscopy. The very efficient trapping of acyl radicals by acyl tellurides themselves is demonstrated by a crossover experiment. Acyl tellurides are shown to participate in very efficient radical cyclization reactions onto alkenes with the formation of five-, six-, and eight-membered rings. The immediate products of the cyclizations onto alkenes are alpha-[(aryltelluro)methyl] ketones and the chemistry of these relatively unstable species is briefly described. Treatment with hydrogen peroxide affords alpha-methylene ketones in high yield. When elimination of the aryl telluro group is not possible the alpha-[(aryltelluro)methyl] ketones are stable species that may subsequently be employed in further radical chain reactions, for example with tributyltin hydride and methyl acrylate. Cyclization onto alkynes yields alpha-[(aryltelluro)methylene] ketones which are stable species and which take part in substitution reactions with higher order cuprates or with diphenyl diselenide.

  DOI：

  10.1021/ja00099a011
• 作为产物：
  描述：

  2-丙-2-烯基硫烷基苯甲酸 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 生成 2-(烯丙基硫基)苯甲酰氯
  参考文献：
  名称：

  Rh催化加氢对烯丙基亚砜的动态动力学拆分：理论和实验相结合的机理研究

  摘要：

  通过将 Mislow [2,3]-σ 重排与催化不对称氢化相结合，证明了烯丙基亚砜的动态动力学拆分 (DKR)。我们的 DKR 的效率通过使用低压氢气来降低相对于 σ 重排速率的氢化速率来优化。动力学研究表明，铑配合物可作为双重催化剂，在催化烯烃氢化的同时加速底物外消旋化。加扰实验和理论模型支持亚砜外消旋的新模式，该模式通过极性溶剂中的铑 π-烯丙基中间体发生。然而，在非极性溶剂中，底物外消旋主要是未催化的。

  DOI：

  10.1021/ja409824b

文献信息

• Carbonyl Radical Cyclizations: Preparation of Some Heterocyclic Ketones
  作者：David Crich、K. Angeline Eustace、Timothy J. Ritchie

  DOI：10.3987/com-88-s27

  日期：——
• US3931318A
  申请人：——

  公开号：US3931318A

  公开（公告）日：1976-01-06
• US4014932A
  申请人：——

  公开号：US4014932A

  公开（公告）日：1977-03-29
• Photoinduced Free Radical Chemistry of the Acyl Tellurides: Generation, Inter- and Intramolecular Trapping, and ESR Spectroscopic Identification of Acyl Radicals
  作者：David Crich、Chen Chen、Jae-Taeg Hwang、Hongwei Yuan、Aristotle Papadatos、Robert I. Walter

  DOI：10.1021/ja00099a011

  日期：1994.10

  Acyl tellurides are prepared in good to excellent yield by the reaction of sodium aryl tellurides with acyl chlorides, or mixed anhydrides, and are found to be moderately air-stable substances. In contrast to previous literature reports, acyl tellurides of aryl and vinyl carboxylic acids are found to be excellent sources of acyl radicals on photolysis with a simple white light source. The acyl radicals so generated may be trapped intermolecularly by dichalcogenides, or by TEMPO in excellent yield. Trapping by N-tert-butyl-alpha-phenyl nitrone produces a stable nitroxide radical which has been characterized by ESR spectroscopy. The very efficient trapping of acyl radicals by acyl tellurides themselves is demonstrated by a crossover experiment. Acyl tellurides are shown to participate in very efficient radical cyclization reactions onto alkenes with the formation of five-, six-, and eight-membered rings. The immediate products of the cyclizations onto alkenes are alpha-[(aryltelluro)methyl] ketones and the chemistry of these relatively unstable species is briefly described. Treatment with hydrogen peroxide affords alpha-methylene ketones in high yield. When elimination of the aryl telluro group is not possible the alpha-[(aryltelluro)methyl] ketones are stable species that may subsequently be employed in further radical chain reactions, for example with tributyltin hydride and methyl acrylate. Cyclization onto alkynes yields alpha-[(aryltelluro)methylene] ketones which are stable species and which take part in substitution reactions with higher order cuprates or with diphenyl diselenide.
• Dynamic Kinetic Resolution of Allylic Sulfoxides by Rh-Catalyzed Hydrogenation: A Combined Theoretical and Experimental Mechanistic Study
  作者：Peter K. Dornan、Kevin G. M. Kou、K. N. Houk、Vy M. Dong

  DOI：10.1021/ja409824b

  日期：2014.1.8

  with catalytic asymmetric hydrogenation. The efficiency of our DKR was optimized by using low pressures of hydrogen gas to decrease the rate of hydrogenation relative to the rate of sigmatropic rearrangement. Kinetic studies reveal that the rhodium complex acts as a dual-role catalyst and accelerates the substrate racemization while catalyzing olefin hydrogenation. Scrambling experiments and theoretical

  通过将 Mislow [2,3]-σ 重排与催化不对称氢化相结合，证明了烯丙基亚砜的动态动力学拆分 (DKR)。我们的 DKR 的效率通过使用低压氢气来降低相对于 σ 重排速率的氢化速率来优化。动力学研究表明，铑配合物可作为双重催化剂，在催化烯烃氢化的同时加速底物外消旋化。加扰实验和理论模型支持亚砜外消旋的新模式，该模式通过极性溶剂中的铑 π-烯丙基中间体发生。然而，在非极性溶剂中，底物外消旋主要是未催化的。