syn-2-[1'-(N-p-chlorophenylamino)-1'-phenyl]methylcyclohexanone

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: syn-2-[1'-(N-p-chlorophenylamino)-1'-phenyl]methylcyclohexanone
• 英文别名: syn-2-((4-chlorophenylamino)(phenyl)methyl)cyclohexanone；2-((4-chlorophenylamino)(phenyl)methyl)cyclohexanone；(2S)-2-[(S)-(4-chloroanilino)-phenylmethyl]cyclohexan-1-one
• 化学式: C₁₉H₂₀ClNO
• 分子量: 313.827
• InChiKey: OIDUARCVRKPECP-IEBWSBKVSA-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 在 2,2,2-三氟乙醇 、 silver trifluoromethanesulfonate 、 对甲苯磺酸 、 N,N-二异丙基乙胺 、 (S)-(-)-5,5-双(二苯膦基)-4,4-双-1,3-苯并间二氧杂环戊烯 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 syn-2-[1'-(N-p-chlorophenylamino)-1'-phenyl]methylcyclohexanone
  参考文献：
  名称：

  通过手性银醇盐催化对映选择性曼尼希型反应

  摘要：

  在2,2,2-三氟乙醇存在下，以SEGPHOS·AgOTf为手性预催化剂，以N，N-二异丙基乙胺为基础预催化剂，实现了三氯乙酸烯基酯与醛亚胺的Mannich型催化不对称反应。通过原位产生的手性烯醇银，以中等至高产率合成选择性地获得了ee高达99％以上的旋光性β-氨基酮。

  DOI：

  10.1021/ol403075u

文献信息

• Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecylsulfate (SDS) Upon a Three-Component Reaction of Aldehydes, Amines, and Ketones Under Neutral Conditions
  作者：Abbas Ali Jafari、Fatemeh Moradgholi、Fatemeh Tamaddon

  DOI：10.1002/ejoc.200801037

  日期：2009.3

  A micellar solution of anionic, cationic or neutral surfactants can be used as an excellent medium for three-component Mannich reactions of aldehydes, amines, and ketones at room temperature. Sodium dodecylsulfate turned out to efficiently catalyze the reaction in neutral pure water (pH ≈ 7), and the corresponding desired β-amino ketones precipitate while the reactions proceedes. This method provides

  阴离子、阳离子或中性表面活性剂的胶束溶液可用作醛、胺和酮在室温下进行三组分曼尼希反应的优良介质。结果证明十二烷基硫酸钠在中性纯水 (pH ≈ 7) 中有效催化反应，并且在反应进行时相应的所需 β-氨基酮沉淀。该方法在温和的反应条件、干净的反应曲线、提高的产率和优异的区域选择性和非对映选择性方面提供了一种新的改进的三组分曼尼希反应，后处理简单。观察到在水中中性条件下点击化学的有趣例子。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• H3PW12O40 supported on silica-encapsulated γ-Fe2O3 nanoparticles: a novel magnetically-recoverable catalyst for three-component Mannich-type reactions in water
  作者：Ezzat Rafiee、Sara Eavani

  DOI：10.1039/c1gc15291b

  日期：——

  A new type of magnetically-recoverable catalyst was synthesized by the immobilization of H3PW12O40 on the surface of silica-encapsulated γ-Fe2O3 nanoparticles. This catalyst was characterized by transmission electron microscopy (TEM), a laser particle size analyzer, infrared spectroscopy (IR) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The results show that the particles are mostly spherical in shape and have an average size of approximately 94 nm. The characterization data derived from IR spectroscopy reveal that H3PW12O40 on the support exists in the Keggin structure. The acidity of the catalyst was measured by a potentiometric titration with n-butylamine. To our surprise, this very strong solid acid catalyst showed an excellent distribution of acid sites, suggesting that the catalyst possesses a higher number of surface active sites compared to its homogeneous analogues. The activity of the catalyst was probed through one-pot three-component Mannich-type reactions of aldehydes, amines and ketones in water at room temperature. The excellent conversions show that the catalyst has strong and sufficient acidic sites, which are responsible for its catalytic performance. After the reaction, the catalyst/product separation could be easily achieved with an external magnetic field, and more than 95% of the catalyst could usually be recovered. The catalyst was reused at least five times without any loss of its high catalytic activity.

  通过将H3PW12O40固定在二氧化硅包覆的γ-Fe2O3纳米颗粒表面，合成了一种新型磁性可回收催化剂。该催化剂通过透射电子显微镜（TEM）、激光粒度分析仪、红外光谱（IR）和电感耦合等离子体原子发射光谱（ICP-AES）进行了表征。结果显示，颗粒主要呈球形，平均尺寸约为94纳米。红外光谱表征数据揭示，负载上的H3PW12O40以Keggin结构存在。催化剂的酸度通过用正丁胺进行的电位滴定法测量。令人惊讶的是，这种非常强的固体酸催化剂显示出优异的酸位点分布，表明催化剂相对于均相类似物具有更高的表面活性位点数量。催化剂的活性通过在水中的室温下进行的一锅法三组分Mannich型反应，即醛、胺和酮的反应来评估。优异的转化率表明，催化剂具有强烈且充分的酸性位点，这是其催化性能的原因。反应后，通过外部磁场可以轻松实现催化剂/产物分离，通常可以回收超过95%的催化剂。该催化剂至少可以重复使用五次，而不会损失其高催化活性。
• 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。
• One-pot three-component Mannich-type reaction catalyzed by trifluoromethanesulfonic acid in water
  作者：Gang Li、Hankui Wu、Zhiyong Wang、Xianli Wang

  DOI：10.1134/s0023158411010113

  日期：2011.2

  One-pot three-component Mannich-type reaction of ketones, aldehydes and amines was efficiently catalyzed by liquid trifluoromethanesulfonic acid in water at ambient temperature. The high yield of corresponding β-amino ketones compounds were achieved. The proposed method is mild, green, simple and efficient.

  在环境温度下，液体三氟甲磺酸在水中能有效地催化酮，醛和胺的一锅三组分曼尼希型反应。实现了高产率的相应β-氨基酮化合物。该方法温和，绿色，简单，有效。
• Mannich reactions catalyzed by perchloric acid in Triton X10 aqueous micelles
  作者：Guo-ping Lu、Chun Cai

  DOI：10.1016/j.catcom.2010.02.007

  日期：2010.3

  Perchloric acid can efficiently catalyze the one-pot, three-component Mannich reactions of ketones with aromatic aldehydes and aromatic amines in Triton X10 aqueous micelles at room temperature. This protocol has several advantages such as excellent yields, mild conditions, clear reaction profile and simple work-up procedure.

  高氯酸可在室温下有效地催化酮与芳族醛和芳族胺的一锅三组分曼尼希反应。该方案具有许多优点，例如产率高，条件温和，反应曲线清晰和后处理程序简单。