2-(苯亚磺酰)-1-苯基乙酮 | 6099-23-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-(苯亚磺酰)-1-苯基乙酮
• 英文名称: 1-(phenylsulfinyl)acetophenone
• 英文别名: 1-phenyl-2-(phenylsulfinyl)ethan-1-one；1-phenyl-2-(phenylsulfinyl)ethanone；Ethanone, 1-phenyl-2-(phenylsulfinyl)-；2-(benzenesulfinyl)-1-phenylethanone
• CAS: 6099-23-6
• 化学式: C₁₄H₁₂O₂S
• 分子量: 244.314
• InChiKey: CGSYWOFFKKJGJV-UHFFFAOYSA-N

物化性质

• 熔点：
  76-77 °C
• 沸点：
  448.0±28.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(苯亚磺酰)-1-苯基乙酮 在 二异丁基氢化铝 、 zinc(II) chloride 作用下， 生成 2-(苯亚磺酰)-1-苯基乙醇
  参考文献：
  名称：

  Chiral sulfur-reagents for the preparation of optically active epoxides

  摘要：

  Acyclic chiral sulfides which could be easily synthesized in both enantiomeric forms leading to poor yields and/or to racemic epoxides, Eliel's oxathiane reagent was used and proved to provide chiral trans diarylepoxides in high yield (70-80%) and enantiomeric purities up to 70-100%, with no rearrangement problems. It was also found that phase-transfer conditions were the easiest and the most efficient for these reactions.

  DOI：

  10.1016/s0040-4020(01)88764-0
• 作为产物：
  描述：

  2-(Benzenesulfinyl)-2-chloro-1-phenylethanol 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以78%的产率得到2-(苯亚磺酰)-1-苯基乙酮
  参考文献：
  名称：

  氯甲基芳基亚砜和醛类合成β-酮基亚砜的新方法

  摘要：

  将氯甲基芳基亚砜的碳负离子加成到醛中得到加合物，将其用三当量的二异丙基氨基锂（LDA）处理，以高总产率得到 β-酮亚砜。

  DOI：

  10.1246/bcsj.63.1266

文献信息

• 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。
• Cu(OTf)₂-Catalyzed Pummerer Coupling of β-Ketosulfoxides
  作者：Regev Parnes、Hagai Reiss、Doron Pappo

  DOI：10.1021/acs.joc.7b02708

  日期：2018.1.19

  The copper(II) trifluoromethanesulfonate-catalyzed Pummerer reaction of β-ketosulfoxides with 1,3-dicarbonyl compounds or π-nucleophiles such as phenols, arenes, and tetraallylsilane is reported. The mild conditions provide an efficient entry to a novel class of polysubstituted 3-alkylthiofuran and polysubstituted 3-thiobenzofuran heterocycles from readily available materials.

  据报道，β-酮亚砜与1,3-二羰基化合物或π-亲核试剂（例如苯酚，芳烃和四烯丙基硅烷）的三氟甲磺酸铜（II）催化Pummerer反应。温和的条件从容易获得的材料中有效地进入了新型的多取代的3-烷基硫呋喃和多取代的3-硫代苯并呋喃杂环。
• A route to benzylic arylsulfoxides from β-ketosulfoxides
  作者：Meng-Yang Chang、Yu-Chieh Cheng、Chieh-Kai Chan

  DOI：10.1016/j.tet.2016.05.038

  日期：2016.7

  The K2CO3-mediated benzylation of β-ketosulfoxides 4 with 2.0 equiv of benzylic halides 5 affords benzylic arylsulfoxides 6 in moderate yields along with trace amounts of chalcones 7. The products 6 are assumed to form in situ intermediates of sulfenate anions from β-ketosulfoxides which are commonly involved in carbon–sulfur bond formation. A plausible mechanism has been proposed.

  用2当量的苄基卤化物5进行的K 2 CO 3介导的β-酮亚砜4的苄基化反应可中等产率地得到苄基芳基亚砜6以及痕量的查耳酮7。假定产物6原位形成了β-酮亚砜中的亚硫酸根阴离子的中间体，这些中间体通常参与碳-硫键的形成。已经提出了一种合理的机制。
• One-pot synthesis of α-phenylsulfinyl ketones by reaction of phenyl benzenethiosulfinate with enolate anions, and synthesis of sulfoxides and sulfides by its reaction with Grignard reagents
  作者：Jerome Fakhry、David H. Grayson

  DOI：10.1016/j.tet.2017.12.028

  日期：2018.2

  give α-phenylsulfinyl ketones directly, together with minor amounts of α-phenylsulfanyl ketones. These are easily separated by forming the water-soluble sodium salts of the sulfinyl compounds. Grignard reagents also react with phenyl benzenethiosulfinate, to give mixtures of sulfoxides and sulfides.

  苯硫基苯磺酸亚砜与源自酮的烯醇酸根阴离子反应，直接生成α-苯硫基酮，以及少量的α-苯硫基酮。通过形成亚磺酰基化合物的水溶性钠盐，可以很容易地将它们分离。格氏试剂也与苯硫基苯磺酸盐反应，生成亚砜和硫化物的混合物。
• PUMMERER REARRANGEMENT PROMOTED BY POLYPHOSPHORIC ACID TRIMETHYLSILYL ESTER (PPSE)
  作者：Masa-aki Kakimoto、Yoshio Imai

  DOI：10.1246/cl.1984.1831

  日期：1984.10.5

  It was found that PPSE catalyzed Pummerer rearrangement of various types of sulfoxides. When α-(phenylsulfinyl)acetophenone was used as sulfoxide, unusual product, phenyl phenylthioglyoxylate was isolated. The reaction seems to proceed via phosphorylation of oxygen of sulfoxides.

  发现PPSE催化各种类型亚砜的Pummerer重排。当α-(苯基亚磺酰基)苯乙酮用作亚砜时，分离出不寻常的产物苯基硫代乙醛酸苯酯。该反应似乎是通过亚砜的氧的磷酸化进行的。