(pyrrolidin-1-yl)(p-tolyl)methanethione | 181970-94-5

• 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: (pyrrolidin-1-yl)(p-tolyl)methanethione
• 英文别名: (4-Methylphenyl)(pyrrolidin-1-yl)methanethione；(4-methylphenyl)-pyrrolidin-1-ylmethanethione
• CAS: 181970-94-5
• 化学式: C₁₂H₁₅NS
• mdl: MFCD03214602
• 分子量: 205.324
• InChiKey: FWPOWOJQUZMIOJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.416
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (pyrrolidin-1-yl)(p-tolyl)methanethione 以 甲醇 、 六甲基磷酰三胺 为溶剂， 生成
  参考文献：
  名称：

  Cyclopalladation of N-(p-thiotoluoyl)pyrrolidine and -piperidine

  摘要：

  Reaction of N-(p-thiotoluoyl)pyrrolidine (Hpr) with lithium tetrachloropalladate(II) in methanol at room temperature resulted in an ortho C-H activation of the benzene ring and a benzene ring-orthopalladated complex PdCl (bpr) was obtained. Another reaction in hexamethylphosphoric triamide at 80 degrees C resulted in an alpha-CH2 activation of the pyrrolidine ring to form PdCl (ppr) with an aliphatic alpha-C-Pd bond. Under the latter reaction conditions N-(p-thiotoluoyl)piperidine (Hpi) was similarly cyclopalladated at alpha-CH2 of the piperidine ring to give PdCl (ppi) but under the former experimental conditions no cyclopalladation occurred. These complexes and some of their derivatives were characterized spectroscopically. The results suggested that the steric bulk of the thioamide-N substituents was of prime importance to cyclopalladation-reactivity of thioamides. To verify the facts, the structures of N-(2-thionaphthoyl)pyrrolidine, Pd(acac) (bpr) (acac = acetylacetonate ion), and {1,3-bis(1-pyrrolidinothiocarbonyl)-phenyl-C-2,S,S'} chloropalladium(II) were determined by X-ray analysis. A pyrrolidino group is a sterically more favorable thioamide-substituent than a dimethylamino group to fulfil the requirements of aromatic ring cyclopalladation of tertiary thioamides with palladium(II). Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0277-5387(96)00105-2
• 作为产物：
  描述：

  1-(4-甲基苯甲酰基)吡咯烷 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以100%的产率得到(pyrrolidin-1-yl)(p-tolyl)methanethione
  参考文献：
  名称：

  衍生自7-氮杂双环[2.2.1]庚烷的硫酰胺的非平面结构。硫酰胺的电子可调平面度。

  摘要：

  X射线晶体学分析表明，与相应的单环吡咯烷硫代酰胺（1a，α= 167.1度和| tau | = 11.2度）相比，N-硫代苯甲酰基-7-氮杂双环[2.2.1]庚烷显示出明显的非平面度（1a，α= 167.1度和| tau | = 11.2度）。在图2a中，alpha = 174.7度，| tau | = 3.9度。在一系列对位取代或未取代的硫代芳酰基-7-氮杂双环[2.2.1]庚烷（1a-1h）中，硫代酰胺的平面度显着取决于取代基的电子性质。例如，在对硝基取代的化合物中，基本上恢复了平面度（1h，α＝ 175.2度，|τ| ＝ 0.1度）。在溶液中，芳族取代基的吸电子特性增加与双环硫代酰胺的更大的旋转势垒有关，通过变温（1）H NMR光谱法和线形分析法测定。硝基苯-d5中1a的旋转势垒降低，即硫酰胺旋转的活化焓（DeltaH（双匕首））降低，与2a在硝基苯-d5中的降低相比，这与1a假定溶

  DOI：

  10.1021/jo801996b

文献信息

• Metal-free three-component synthesis of thioamides from β-nitrostyrenes, amines and elemental sulfur
  作者：Ling Peng、Li Ma、Ying Ran、Yunfeng Chen、Zhigang Zeng

  DOI：10.1016/j.tetlet.2021.153092

  日期：2021.6

  A metal-free CC bond cleavage reaction of β-nitrostyrenes in the presence of elemental sulfur and secondary amines/amides is described. Elemental sulfur serves as both a raw material and an oxidant for CC bond cleavage, and secondary amines or amides are both feasible nitrogen sources. Besides mild reaction condition and simple work-up procedure, the method provided thioamides with good to excellent

  描述了在元素硫和仲胺/酰胺存在下 β-硝基苯乙烯的无金属 C C 键裂解反应。元素硫既是C C 键断裂的原料又是氧化剂，仲胺或酰胺都是可行的氮源。除了温和的反应条件和简单的后处理程序外，该方法还提供了具有良好收率的硫代酰胺。
• Leveraging the Domino Skeletal Expansion of Thia-/Selenazolidinones via Nitrogen-Atom Transfer in Hexafluoroisopropanol: Room Temperature Access to Six-Membered S/Se,N-Heterocycles
  作者：Vandana Jaiswal、Mangilal Godara、Dinabandhu Das、Vincent Gandon、Jaideep Saha

  DOI：10.1021/acs.joc.1c02621

  日期：2022.1.7

  Herein, a highly regioselective domino skeletal-expansion process that transforms 2-aminothiazolidinone into six-membered S,N-heterocycle is developed with the aid of TMS-azide in hexafluoroisopropanol (HFIP) at ambient temperature. Functioning of the C2 tertiary amine as latent reactive group on thiazolidinone moiety was the key to this development, which allowed relay substitution with azide and

  在此，在环境温度下，在六氟异丙醇 (HFIP) 中借助 TMS-叠氮化物，开发了一种高度区域选择性的多米诺骨架扩展工艺，该工艺将 2-氨基噻唑烷酮转化为六元 S，N-杂环。C2 叔胺作为噻唑烷酮部分上的潜在反应基团的功能是这一发展的关键，它允许用叠氮化物进行接力取代，并在无金属/酸的条件下进行后续的扩环。该反应还强调了从 TMS-叠氮化物到最终产物的分子间氮原子转移过程，其中不存在任何中间体叠氮噻唑烷酮。该策略可扩展到Se,N-杂环的类似合成，此外，还进行了后期药物修饰和后续转化。
• Ruthenium(II)-Catalyzed C–H Arylation of N,N-Dialkyl Thiobenzamides with Boronic Acids by Sulfur Coordination in 2-MeTHF
  作者：Jin Zhang、Ying Liu、Qiangqiang Jia、Yue Wang、Yangmin Ma、Michal Szostak

  DOI：10.1021/acs.orglett.0c02410

  日期：2020.9.4

  We report ruthenium(II)-catalyzed ortho-C–H arylation of N,N-dialkylthiobenzamides with boronic acids. The method employs [RuCl2(p-cym)]2 in the presence of Cu(OTf)2 and Ag2O oxidant. The reaction represents the first example of Ru-catalyzed C–H arylation directed by sulfur-containing groups and a rare example of C–H arylation directed by the versatile thiobenzamide moiety. As a further advantage,

  我们报道了钌（II）催化N，N-二烷基硫代苯甲酰胺与硼酸的邻位-C–H芳基化。该方法在Cu（OTf）2和Ag 2 O氧化剂存在下使用[RuCl 2（p -cym）] 2。该反应代表了由含硫基团引导的Ru催化C–H芳基化的第一个实例，以及由多用途硫代苯甲酰胺部分引导的C–H芳基化的罕见实例。作为另一优点，该方法在可持续且生态友好的2-MeTHF作为溶剂中进行。
• Cobalt(<scp>iii</scp>)-catalyzed C–H amidation of <i>N</i>,<i>N</i>-dialkyl thiobenzamides by sulfur coordination
  作者：Pengpeng Gao、Xiaohui Zhang、Qing-Zhong Zheng

  DOI：10.1039/d1ob02034j

  日期：——

  An efficient inexpensive cobalt(III)-catalyzed intermolecular amidation of N,N-dialkyl thiobenzamides with 1,4,2-dioxazol-5-ones via C–H bond activation is described. The reaction proceeds with high functional group tolerance under external oxidant free conditions, providing a straightforward approach for the direct modification of thioamide derivatives, which are prevalent organic motifs found in

  描述了一种通过C-H 键活化的高效廉价钴 ( III ) 催化的N,N-二烷基硫代苯甲酰胺与 1,4,2-二恶唑-5-酮的分子间酰胺化。该反应在无外部氧化剂条件下以高官能团耐受性进行，为直接修饰硫代酰胺衍生物提供了一种直接的方法，硫代酰胺衍生物是重要的生物和药物分子中普遍存在的有机基序。
• Benzotriazole-Assisted Thioacylation
  作者：Alan R. Katritzky、Rachel M. Witek、Valerie Rodriguez-Garcia、Prabhu P. Mohapatra、James W. Rogers、Janet Cusido、Ashraf A. A. Abdel-Fattah、Peter J. Steel

  DOI：10.1021/jo050670t

  日期：2005.9.1

  Benzotriazole reagents for thioacylation (RCSBt), thiocarbamoylation (RR'NCSBt), aryl/alkoxythioacylation (ROCSBt), and aryl/alkylthiothioacylation (RSCSBt) are synthesized, and their utility is assessed by syntheses of representative heteroaryl thioureas 3a-g, thioamides 15a-s, thionoesters 16a-h, thiocarbamates 17a-e, dithiocarbamates 18a-d, thiocarbonates 19a-c, and dithiocarbonates 20a-c.