1-(4-chlorophenyl)-2-(piperidin-1-yl)-2-thioxoethanone | 128592-66-5

• 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: 1-(4-chlorophenyl)-2-(piperidin-1-yl)-2-thioxoethanone
• 英文别名: 1-(4-Chlorophenyl)-2-piperidin-1-yl-2-sulfanylideneethanone
• CAS: 128592-66-5
• 化学式: C₁₃H₁₄ClNOS
• 分子量: 267.779
• InChiKey: YIUJHRLBNTXNEB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  52.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2'-溴-4-氯苯乙酮 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 sodium azide 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 1.0h， 生成 1-(4-chlorophenyl)-2-(piperidin-1-yl)-2-thioxoethanone
  参考文献：
  名称：

  α-叠氮基酮的无金属CN或CC键裂解：α-酮硫代酰胺和酰胺合成的氧化酰胺化策略。

  摘要：

  提出了一种新型的无金属氧化酰胺化策略，用于由α-叠氮基酮合成α-酮硫代酰胺和酰胺。α-叠氮基酮的CH键与元素硫的硫键化可形成α-酮硫代酰基叠氮化物，然后被胺类亲核攻击，导致CN键断裂，生成α-酮硫代酰胺，而酰胺可随氮的释放而形成。 PhI（OAc）2存在下通过选择性CC键裂解产生的气体和氰基阴离子。

  DOI：

  10.1021/acs.joc.9b01777

文献信息

• Willgerodt–Kindler reaction of arylglyoxals with amines and sulfur in aqueous media: a simple and efficient synthesis of α-ketothioamides
  作者：Bagher Eftekhari-Sis、Saleh Vahdati-Khajeh、S. Motahhareh Amini、Maryam Zirak、Mahnaz Saraei

  DOI：10.1080/17415993.2012.757614

  日期：2013.10.1

  A simple and efficient method for the synthesis of α-ketothioamides via the Willgerodt–Kindler reaction is developed. Reactions were carried out between arylglyoxal hydrates, amines and elemental sulfur in water at 80°C to afford corresponding α-ketothioamides in good to high yields in a short reaction time.

  开发了一种通过 Willgerodt-Kindler 反应合成 α-酮硫酰胺的简单有效的方法。芳基乙二醛水合物、胺和元素硫在 80°C 的水中进行反应，在较短的反应时间内以良好至高产率得到相应的 α-酮硫代酰胺。
• A study of the Willgerodt–Kindler reaction to obtain thioamides and α-ketothioamides under solvent-less conditions
  作者：José Ernesto Valdez-Rojas、Hulme Ríos-Guerra、Alma Leticia Ramírez-Sánchez、Guadalupe García-González、Cecilio Álvarez-Toledano、José Guadalupe López-Cortés、Rubén A. Toscano、José Guillermo Penieres-Carrillo

  DOI：10.1139/v2012-030

  日期：2012.7

  In this paper, the results obtained in the synthesis of thioamides and α-ketothioamides by a modification of the Willgerodt–Kindler reaction, under solvent-free and noncatalyst conditions using IR energy as a source of activation, are presented. The use of IR energy in these reactions has been shown to lead to a mixture of thioamide and α-ketothioamide as the main products in most cases, with the latter predominating. The yields of α-ketothioamides from most of these reactions are better than those reported previously. To the best of our knowledge, this is the first time that IR energy has been applied to promote the Willgerodt–Kindler reaction.

  在这篇论文中，通过对Willgerodt-Kindler反应进行改进，在无溶剂和非催化剂条件下利用红外能作为激活源合成了硫代酰胺和α-酮硫代酰胺。这些反应中使用红外能已被证明通常会导致硫代酰胺和α-酮硫代酰胺的混合物作为主要产物，后者占主导地位。这些反应中大多数情况下得到的α-酮硫代酰胺产率优于先前报道的结果。据我们所知，这是首次应用红外能促进Willgerodt-Kindler反应。
• Reactions of diphenacylaniline and diphenacyl sulfide under Gewald conditions: generation of enamines and thioamides
  作者：Nidhin Paul、Ramalingam Sathishkumar、Chellathurai Anuba、Shanmugam Muthusubramanian

  DOI：10.1039/c3ra21556c

  日期：——

  The 1,5-diketone, diphenacylaniline, yielded an enamine under Gewald conditions, while another 1,5-diketone, diphenacyl sulfide, resulted in thioamide formation under identical conditions. 2-Amino-4-(3-oxo-1,3-diphenylpropyl)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile was obtained from the 1,5-diketone 2-(3-oxo-1,3-diphenylpropyl)-1-cyclohexanone under the same conditions.

  在格瓦尔德条件下，1,5-二酮--二苯基苯胺生成了烯胺，而另一种 1,5- 二酮--二苯基硫醚在相同条件下生成了硫代酰胺。在相同的条件下，2-(3-氧代-1,3-二苯基丙基)-4,5,6,7-四氢苯并[b]噻吩-3-甲腈从 1,5-二酮 2-(3-氧代-1,3-二苯基丙基)-1-环己酮中得到。
• Metal-free oxidative coupling of aryl acetylene with elemental sulphur and amines: facile access to α-ketothioamides
  作者：Deepika Sharma、Rana Chatterjee、Vasudevan Dhayalan、Rambabu Dandela

  DOI：10.1039/d4ob00830h

  日期：——

  A simple and efficient oxidative coupling of aromatic alkynes with elemental sulphur and secondary amines has been reported. The iodine/DMSO system easily promoted the transformations, affording thioglyoxamides via C–S, C–O, and C–N bond formations. In this context, acetylenic C–H bond oxidation has occurred through iodination, leading to the desired products. Moreover, this metal-free, one-pot protocol

  据报道，芳族炔烃与元素硫和仲胺发生简单而有效的氧化偶联。碘/DMSO 系统很容易促进转化，通过C-S、C-O 和 C-N 键形成提供硫代乙二酰胺。在这种情况下，通过碘化发生了炔属C-H键氧化，产生了所需的产物。此外，这种无金属的一锅法方案是通过使用容易获得的起始原料，在没有外部氧化剂的情况下，在有氧条件下完成的，以中等至良好的产率提供各种α-酮硫酰胺化合物。
• Synthesis of α-Ketothioamides via Willgerodt-Kindler Reaction of Arylglyoxals with Amines and Sulfur under Solvent-Free Conditions
  作者：Bagher Eftekhari-Sis、Saleh Khajeh、Orhan Büyükgüngör

  DOI：10.1055/s-0032-1316897

  日期：——

  Willgerodt-Kindler reaction of arylglyoxal hydrates with secondary amines and elemental sulfur under solvent-free conditions at 80 degrees C is developed, in which alpha-ketothioamides are obtained in 70-90% yield in 0.6-1 hour. The X-ray crystal-structure analysis for one compound was obtained.