(2SR)-2-[(RS)-(2-chlorophenyl)(phenylamino)methyl]cyclohexanone

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2SR)-2-[(RS)-(2-chlorophenyl)(phenylamino)methyl]cyclohexanone
• 英文别名: 2-((2-chlorophenyl)(phenylamino)methyl)cyclohexanone；2-((2-chlorophenyl)(phenylamino)methyl)cyclohexan-1-one；rac-(S)-2-((R)-(2-chlorophenyl)(phenylamino)methyl)cyclohexanone；(2R)-2-[(S)-anilino-(2-chlorophenyl)methyl]cyclohexan-1-one
• 化学式: C₁₉H₂₀ClNO
• 分子量: 313.827
• InChiKey: BMOUBCNNDYGPCB-QFBILLFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  环己酮 、 2-氯苯甲醛 、 苯胺 在 polymeric laponite nanoclay 作用下， 以 neat (no solvent) 为溶剂， 反应 2.0h， 以75%的产率得到(2SR)-2-[(RS)-(2-chlorophenyl)(phenylamino)methyl]cyclohexanone
  参考文献：
  名称：

  合成锂皂石纳米粘土催化剂直接催化环酮的曼尼希型反应的非对映选择性

  摘要：

  开发了一种基于HPMC（羟丙基甲基纤维素）的新型聚合锂皂石纳米粘土多相催化体系，用于酮与取代的苯甲醛和苯胺的直接曼尼希式反应，从而以高至高收率提供相应的β-氨基酮。有趣的是，环状酮表现出不同的化学选择性。环戊烷酮进行羟醛缩合反应生成交联的羟醛产物，而环己酮和环戊酮则得到相应的曼尼希加合物。在环己酮的情况下，立体选择性随苯甲醛上取代基的性质而变化，其中适度的供电子和吸电子基团提供了抗异构体为主要产物，但强供电子的取代苯甲醛导致合成异构体为主要的曼尼希加合物。曼尼希与环庚酮的反应导致曼尼希加合物具有出色的顺式选择性。

  DOI：

  10.1007/s13738-015-0772-z

文献信息

• 5-Sulfosalicylic acid catalyzed direct Mannich reaction in pure water
  作者：Chun Chen、Xuyang Zhu、Ya Wu、Huaming Sun、Guofang Zhang、Weiqiang Zhang、Ziwei Gao

  DOI：10.1016/j.molcata.2014.08.017

  日期：2014.12

  A water-soluble Brønsted acid, 5-sulfosalicylic acid, efficiently catalyzed the direct three-component Mannich reactions of cyclohexanone and 3-pentanone in pure water. 21 Examples of Mannich reactions were presented, which afforded the corresponding β-amino ketones with up to 97% yield and decent diastereoselectivities. The acid catalyst can be recycled as an aqueous solution for at least six times

  水溶性布朗斯台德酸5-磺基水杨酸可在纯水中有效催化环己酮和3-戊酮的直接三组分曼尼希反应。给出了21个Mannich反应的例子，该例子提供了相应的β-氨基酮，产率高达97％，非对映选择性也不错。酸催化剂可以水溶液形式循环至少六次，曼尼希产品的产率保持在90％以上。
• Synthesis of air-stable mixed bis-carboxylate titanocene complexes and their catalytic behaviors in cross-aldol and Mannich reactions
  作者：Jing Wang、Xi Chen、Xiu Wang、Wei-Qiang Zhang、Hua-Ming Sun、Guo-Fang Zhang、Ya Wu、Zi-Wei Gao

  DOI：10.1007/s11243-016-0054-3

  日期：2016.10

  Abstract Tunable organometallic Lewis acid catalysts were developed by combining salicylic acid (H2-Sal) with benzoic acid (H-Ben), 4-fluorobenzoic acid (H-BenF) and 3-thiophenic acid (H-Th), as coligands for mixed bis-carboxylate titanocene complexes. Three air-stable complexes [Cp2Ti(η1-HSal)(η1-Ben)] (1), [Cp2Ti(η1-HSal)(η1-BenF)] (2) and [Cp2Ti[η1-HSal][(η1-Th)] (3) were prepared in high yields

  摘要 以水杨酸 (H2-Sal) 与苯甲酸 (H-Ben)、4-氟苯甲酸 (H-BenF) 和 3-噻吩酸 (H-Th) 作为混合配体，开发了可调有机金属路易斯酸催化剂。双羧酸二茂钛络合物。三种空气稳定配合物 [Cp2Ti(η1-HSal)(η1-Ben)] (1), [Cp2Ti(η1-HSal)(η1-BenF)] (2) 和 [Cp2Ti[η1-HSal][(η1- Th)] (3) 通过水杨酸二茂钛螯合物与羧酸盐配体的反应以高产率制备。通过物理化学和光谱方法充分表征了混合的双羧酸二茂钛配合物。单晶 X 射线衍射研究揭示了 Ti-O(H-Sal) 键距分别为 1.972(3)、1.9245(18) 和 1.912(5) Å，而键距涉及1、2 和 3 的配体为 1.908(3) Å (Ti-OBen)、1.9296(19) Å (Ti-OBenF) 和 1。分别为 945(5) Å (
• Highly Selective Synthesis of β-Amino Carbonyl Compounds over ZSM-5-SO₃H under Solvent-free Conditions
  作者：Ahmad Reza Massah、Roozbeh Javad Kalbasi、Neda Samah

  DOI：10.5012/bkcs.2011.32.5.1703

  日期：2011.5.20

  ZSM-5-$SO_3H$ efficiently catalyzed the one-pot three-component Mannich reaction of aldehydes, anilines, and ketones. $\beta}$-Aminocarbonyl compounds were obtained in reasonable yields and excellent stereoselectivities when the reaction was carried out at room temperature under solvent-free conditions. Simple experimental conditions and product isolation procedure makes this protocol potential for the development of clean and environment-friendly strategy for the synthesis of $\beta}$-amino-ketones. The catalyst was recovered and reused for subsequent runs.

  ZSM-5-$SO_3H$可高效催化醛、苯胺和酮的一锅三组分曼尼希反应。$beta}$-氨基羰基化合物在室温无溶剂条件下进行反应时，产量合理，立体选择性极佳。简单的实验条件和产物分离步骤使该方法有望发展成清洁环保的$\beta}$-氨基酮合成策略。催化剂被回收并重复用于后续操作。
• Aqueous formic acid: an efficient, inexpensive and environmentally friendly catalyst for diastereoselective synthesis of β-amino carbonyl derivatives
  作者：Hossein Ghafuri、Samaneh Khodashenas、Mohammad Reza Naimi-Jamal

  DOI：10.1007/s13738-014-0517-4

  日期：2015.4

  In this article, we present a convenient and green method for synthesis of β-amino carbonyl compounds through ball-milling technique by using aqueous formic acid, which is an inexpensive and highly efficient catalyst. This multi-component reaction was done at room temperature with high anti-selectivity and easy workup. The use of solvent-free ball-milling technique helped to have high yields and more cleanness, besides omitting the need for solvent in this method.

  本文介绍了一种利用甲酸水溶液这种廉价高效催化剂，通过球磨技术合成β-氨基羰基化合物的便捷绿色方法。这种多组分反应在室温下进行，具有高抗选择性和易操作性。无溶剂球磨技术的使用有助于获得高产率和更高的清洁度，此外，这种方法还省去了溶剂。
• H₃PW₁₂O₄₀supported on functionalized polyoxometalate organic–inorganic hybrid nanoparticles as efficient catalysts for three-component Mannich-type reactions in water
  作者：Roushan Khoshnavazi、Leila Bahrami、Forugh Havasi、Elham Naseri

  DOI：10.1039/c6ra27519b

  日期：——

  results show that the particles are mostly spherical in shape and have an average size in the range of 20–50 nm. The catalytic activities of the catalysts were probed through one-pot three-component Mannich-type reactions of aldehydes, amines and ketones in water at room temperature. The catalysts were re-used at least five times without any loss of their high catalytic activity.

  通过将H 3 PW 12 O 40（HPW 12）固定在H 6 Cu 2 [PPDA] 6 [SiW 9 Cu 3 O 37 ]·12H 2的有机-无机多金属氧酸盐纳米颗粒的表面上，合成了两种新型催化剂。O（HybPOM）（PPDA =对苯二胺）和Go / Fe 3 O 4/ HybPOM纳米粒子。这些催化剂的特征在于热重分析（TGA），傅立叶变换红外（FT-IR）光谱，扫描电子显微镜（SEM），能量色散X射线分析（EDX）和交替梯度力磁力法（AGFM）。红外光谱和XRPD揭示HPW 12固定在支持物上。用n进行电位滴定丁胺表明该催化剂可分类为强酸。结果表明，这些粒子大多为球形，平均大小在20–50 nm范围内。在室温下通过醛，胺和酮的一锅三组分曼尼希型反应来探测催化剂的催化活性。催化剂可重复使用至少五次，而不会损失其高催化活性。