2,5-dichlorothiophene 1,1-dioxide | 72541-87-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 2,5-dichlorothiophene 1,1-dioxide
• 英文别名: 2,5-dichlorothiophene S,S-dioxide；2,5-dichlorothiophene-1,1-dioxide
• CAS: 72541-87-8
• 化学式: C₄H₂Cl₂O₂S
• 分子量: 185.031
• InChiKey: ZYNDDSQKVZHUNR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-methylphenylaminofulvene 、 2,5-dichlorothiophene 1,1-dioxide 以 四氢呋喃 为溶剂， 以14%的产率得到4,7-dichloroazulene
  参考文献：
  名称：

  [6+4] 受体噻吩二氧化物的环加成反应：取代芴的合成

  摘要：

  摘要 [6+4] 官能化的二氧化噻吩与各种富烯的环加成反应提供了相应的芴。观察到的区域化学是根据 HOMO-LUMO 轨道系数来解释的。

  DOI：

  10.1007/s11172-006-0227-x
• 作为产物：
  描述：

  2,5-二氯噻吩 在 双氧水 、 三氟乙酸酐 作用下， 以 乙腈 为溶剂， 以76%的产率得到2,5-dichlorothiophene 1,1-dioxide
  参考文献：
  名称：

  带有吸电子基团的噻吩-1,1-二氧化物的简便方法

  摘要：

  迄今为止，尚未描述具有强EWG的噻吩-1,1-二氧化物的通用合成方法。乙腈中不存在水的三氟过氧乙酸可氧化噻吩，包括具有吸电子基团的实例，如磺酰基或烷氧基羰基。开发了一种容易且可按比例放大的程序，获得了一些以前未知的噻吩-1,1-二氧化物。

  DOI：

  10.1016/s0040-4039(01)00732-8

文献信息

• Reactions of electron-withdrawing thiophene 1,1-dioxides with furans. A novel reaction pathway
  作者：A. M. Moiseev、E. S. Balenkova、V. G. Nenajdenko

  DOI：10.1007/s11172-006-0318-8

  日期：2006.4

  Reactions of thiophene dioxides containing electron-withdrawing substituents with furans were studied. The reactions with unsubstituted furan followed the inverse-electron-demand Diels-Alder mechanism. Subsequent elimination of sulfur dioxide from the adduct afforded products of the tetrahydrobenzofuran series. The reactions with substituted furans gave benzylcarbonyl compounds in high yields. The

  研究了含有吸电子取代基的二氧化噻吩与呋喃的反应。与未取代呋喃的反应遵循逆电子需求 Diels-Alder 机制。随后从加合物中消除二氧化硫，得到四氢苯并呋喃系列的产物。与取代的呋喃反应以高产率得到苄基羰基化合物。使用计算的轨道系数，根据前沿轨道理论解释了观察到的反应区域化学。
• A novel oxidation of thiophenes using HOF·MeCN
  作者：Shlomo Rozen、Yifat Bareket

  DOI：10.1039/c39940001959

  日期：——

  The complex, HOF·MeCN made directly by bubbling fluorine through aqueous MeCN, oxidizes various types of thiophenes to the corresponding S,S-dioxides, including ones which could not be oxidized by any other method.

  该复合物HOF·MeCN通过将氟气通入水性MeCN中直接制得，能够将各种类型的噻吩氧化为相应的S,S-二氧化物，其中包括那些无法通过其他任何方法氧化的噻吩。
• A facile route to thiophene-1,1-dioxides bearing electron-withdrawing groups
  作者：Valentine G Nenajdenko、Andrew E Gavryushin、Elizabeth S Balenkova

  DOI：10.1016/s0040-4039(01)00732-8

  日期：2001.6

  thiophene-1,1-dioxides with strong EWGs has been described to date. Trifluoroperacetic acid in acetonitrile in the absence of water is shown to oxidise thiophenes, including examples possessing an electron-withdrawing group such as sulfonyl or alkoxycarbonyl. An easy and ready for scale-up procedure is developed, some formerly unknown thiophene-1,1-dioxides are obtained.

  迄今为止，尚未描述具有强EWG的噻吩-1,1-二氧化物的通用合成方法。乙腈中不存在水的三氟过氧乙酸可氧化噻吩，包括具有吸电子基团的实例，如磺酰基或烷氧基羰基。开发了一种容易且可按比例放大的程序，获得了一些以前未知的噻吩-1,1-二氧化物。
• De Novo Synthesis of Dihydrobenzofurans and Indolines and Its Application to a Modular, Asymmetric Synthesis of Beraprost
  作者：Ze-Shu Wang、Steven H. Bennett、Bilal Kicin、Changcheng Jing、Johan A. Pradeilles、Karen Thai、James R. Smith、P. David Bacoş、Valerio Fasano、Carla M. Saunders、Varinder K. Aggarwal

  DOI：10.1021/jacs.3c04582

  日期：2023.6.28

  investigation of this step using deuterium-labeling studies indicated the intermediacy of a carbene which undergoes a 1,2-hydrogen shift and subsequent aromatization. The methodology was applied to a modular and stereoselective total synthesis of the antiplatelet drug beraprost in only 8 steps from a key enal-lactone. This lactone provided the core of beraprost to which both its sidechains could be appended

  二氢苯并呋喃和二氢吲哚是药物的重要成分。在这里，我们描述了一种新的构建策略，其中芳香环是从头创建的通过反电子需求狄尔斯-阿尔德反应和 2-卤代噻吩-1,1-二氧化物与烯醇醚/烯酰胺的螯合挤出序列，然后进行芳构化。不同寻常的是，芳构化过程被证明是非常具有挑战性的，但人们发现用碱处理卤代环己二烯会影响α-消除-芳构化反应。使用氘标记研究对该步骤的机理研究表明卡宾的中间作用，该卡宾经历 1,2-氢转移和随后的芳构化。该方法被应用于抗血小板药物贝前列素的模块化和立体选择性全合成，仅需 8 个步骤即可从关键的烯内酯合成。该内酯提供了贝前列素的核心，其两个侧链可以通过 1,4-共轭加成过程（较低的 ω-侧链）附加到该核心，使用我们新开发的方法从头构建贝前列素的二氢苯并呋喃（上部 α-侧链）。此外，我们还展示了我们新建立的方案在功能化二氢吲哚合成中的广度，这是在高水平的区域控制下发生的。根据密度泛函理论
• Oxidation of Sulfur-Containing Compounds with HOF·CH₃CN
  作者：Shlomo Rozen、Yifat Bareket

  DOI：10.1021/jo961862e

  日期：1997.3.1

  The HOF . CH3CN complex, easily prepared by passing F-2 through aqueous acetonitrile, is an exceptionally efficient oxygen transfer agent. All types of sulfides have been oxidized to sulfones in excellent yields, in a few minutes at room temperature. The reaction proceeds through the formation of sulfoxides which at low temperatures of around -75 degrees C could be isolated in good yields. It was demonstrated through a reaction with thianthrene 5-oxide (20) that HOF . CH3CN is strongly electrophilic in nature. Sulfides with an electron-depleted sulfur atom such as perfluoroalkyl or aryl sulfides, which could not be well oxidized by any other method, were also efficiently converted to the corresponding sulfones in minutes. Thiophenes are generally hard to oxidize to the corresponding S-dioxides since the conditions required by the orthodox oxidants encourage consecutive typical ene and diene reactions. HOF . CH3CN requires;short reaction times and low temperatures, thus enabling the isolation of thiophene dioxides, some of which could not be made by any other way. It seems that apart from unprotected amines, other functional groups such as aromatic rings, ketones, hydroxyls, and ethers do not interfere, since the sulfur atom reacts considerably faster.