3-(4-fluorobenzylidene)-2-piperidone | 607731-27-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-(4-fluorobenzylidene)-2-piperidone
• 英文别名: 3-(4-fluorobenzylidene)piperidin-2-one；3-(p-fluorobenzylidene)-2-piperidone；3-[(4-Fluorophenyl)methylidene]piperidin-2-one
• CAS: 607731-27-1
• 化学式: C₁₂H₁₂FNO
• 分子量: 205.232
• InChiKey: BLKNAAHKUZGRNB-UHFFFAOYSA-N

物化性质

• 熔点：
  170 °C
• 沸点：
  405.6±45.0 °C(Predicted)
• 密度：
  1.200±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(4-fluorobenzylidene)-2-piperidone 在 lithium aluminium tetrahydride 、 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 15.0~30.0 ℃ 、480.55 kPa 条件下， 反应 8.0h， 生成 3-(4-氟苄基)-哌啶
  参考文献：
  名称：

  Stereoselective Process for a CCR3 Antagonist

  摘要：

  A convergent, multikilogram, stereoselective synthesis of 1 is described. A key fragment, (S)-3-(4-fluorobenzyl)piperidine (2) was synthesized from valerolactam in three steps using our recently discovered Ir-BDPP-catalyzed asymmetric hydrogenation. Another key fragment, (IR,2R)-2-(benzyloxycarbonylamino)cyclohexanecarboxaldehyde (3) was synthesized from meso-hexahydrophthalic anhydride in seven steps. The stereochemistry was set in the first step of this sequence via a quinidine-mediated desymmetrization of the meso-anhydride. Coupling of the fragments 2 and 3 followed by deprotection provided the penultimate 23. The active pharmaceutical ingredient (API) free base I was obtained by treatment of 23 with the aminothiazole fragment 4 under mild conditions.

  DOI：

  10.1021/op050202l
• 作为产物：
  描述：

  哌啶酮 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲苯 、 叔丁醇 为溶剂， 反应 2.5h， 生成 3-(4-fluorobenzylidene)-2-piperidone
  参考文献：
  名称：

  Stereoselective Process for a CCR3 Antagonist

  摘要：

  A convergent, multikilogram, stereoselective synthesis of 1 is described. A key fragment, (S)-3-(4-fluorobenzyl)piperidine (2) was synthesized from valerolactam in three steps using our recently discovered Ir-BDPP-catalyzed asymmetric hydrogenation. Another key fragment, (IR,2R)-2-(benzyloxycarbonylamino)cyclohexanecarboxaldehyde (3) was synthesized from meso-hexahydrophthalic anhydride in seven steps. The stereochemistry was set in the first step of this sequence via a quinidine-mediated desymmetrization of the meso-anhydride. Coupling of the fragments 2 and 3 followed by deprotection provided the penultimate 23. The active pharmaceutical ingredient (API) free base I was obtained by treatment of 23 with the aminothiazole fragment 4 under mild conditions.

  DOI：

  10.1021/op050202l

文献信息

• Chemical‐Reductant‐Free Electrochemical Deuteration Reaction using Deuterium Oxide
  作者：Xu Liu、Ruoyu Liu、Jiaxing Qiu、Xu Cheng、Guigen Li

  DOI：10.1002/anie.202005765

  日期：2020.8.10

  We report a method for the electrochemical deuteration of α,β‐unsaturated carbonyl compounds under catalyst‐ and external‐reductant‐free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external

  我们报告了一种在无催化剂和无外部还原剂的条件下对α，β-不饱和羰基化合物进行电化学氘化的方法，氘化率高达99％，在2小时内产率高达91％。阴极和阳极同时使用石墨毡是确保在中性条件下无需外部还原剂的情况下化学选择性和高氘掺入的关键。与先前报道的使用化学计量的金属还原剂的氘代反应相比，该方法具有许多优点。机理实验表明，阳极处的O 2析出不仅消除了对外部还原剂的需求，而且还调节了反应混合物的pH值，使其保持中性。
• Gold(I)-Catalysed Hydroarylation of Lactam-Derived Enynes as an Entry to Tetrahydrobenzo[<i>g</i> ]quinolines
  作者：Stefano Nejrotti、Simone Ghinato、Elena C. Gini、Dina Scarpi、Ernesto G. Occhiato、Andrea Maranzana、Cristina Prandi

  DOI：10.1002/ejoc.201901599

  日期：2020.2.14

  The gold(I)‐catalysed cyclization of N‐tosyl‐protected 5‐benzyl‐6‐((trimethylsilyl)ethynyl)‐1,2,3,4‐tetrahydropyridines, prepared by Sonogashira coupling of lactam‐derived enol triflates, provides tetrahydrobenzo[g]quinolones. The Au(I)‐catalysed reaction is carried out with (C6F5)3PAuCl/AgNTf2 and proceeds via a 6‐exo‐dig cyclization to the aromatic tetrahydrobenzo[g]quinolines. The mode of cyclization

  由内酰胺衍生的烯醇三氟甲磺酸钠的Sonogashira偶合制备的金（I）催化的N-甲苯磺酰基保护的5-苄基-6-（（（三甲基甲硅烷基）乙炔基）1,2,3,4-四氢吡啶的环化反应提供四氢苯并[ g ]喹诺酮类。在Au（I） -催化的反应是用（C进行6 ˚F 5）3 PAuCl / AgNTf 2经由6-并且进行外切-挖环化为芳族四氢苯并[克]喹啉。DFT计算讨论并支持了环化模式。
• Process for the manufacture of optically active 3-substituted lactams by asymmetric hydrogenation of 3-alkylidenelactams
  申请人：——

  公开号：US20040010139A1

  公开（公告）日：2004-01-15

  The present invention relates generally to processes for the efficient production optically active 3-substituted lactams of formula (I) 1 process, comprising: contacting a compound of formula (II): 2 with hydrogen under a suitable pressure in the presence of an iridium complex of the formula (R 2 )IrL + X − wherein L is a chelating diene, X is a non coordinating anion, and R 2 is selected from 3

  本发明通常涉及一种高效生产光学活性的3-取代内酰胺的方法，其中包括：将式（II）的化合物与氢在适当压力下在(R2)IrL+X−的铱配合物存在下接触，其中L是螯合二烯，X是非配位阴离子，R2是选择自3。