2-氧代-1-(3-氧代环己基)环戊烷-1-羧酸乙酯 | 170969-99-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2-氧代-1-(3-氧代环己基)环戊烷-1-羧酸乙酯
• 英文名称: ethyl 2-oxo-1-(3-oxocyclohexyl)-cyclopentanecarboxylate
• 英文别名: Cyclopentanecarboxylic acid, 2-oxo-1-(3-oxocyclohexyl)-, ethyl ester；ethyl 2-oxo-1-(3-oxocyclohexyl)cyclopentane-1-carboxylate
• CAS: 170969-99-0
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: HGBWVALBOQUXST-UHFFFAOYSA-N

物化性质

• 沸点：
  376.8±42.0 °C(Predicted)
• 密度：
  1.177±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-环己烯-1-酮 、 2-氧代环戊羧酸乙酯 在 六甲基磷酰三胺 、 lithium chloride 作用下， 生成 2-氧代-1-(3-氧代环己基)环戊烷-1-羧酸乙酯
  参考文献：
  名称：

  A New Method for the Preparation of Michael Adducts and Cyclic Enones Using Lithium Chloride-Hexamethylphosphoramide System.

  摘要：

  一种使用氯化锂和六甲基磷酰胺的新程序被发现对迈克尔型加成物和环己烯酮的合成非常有用。通过改变反应温度，可以控制两种产品的选择性。此外，还研究了以脲类溶剂替代六甲基磷酰胺的情况。

  DOI：

  10.1248/cpb.43.734

文献信息

• Highly Efficient C−C Bond-Forming Reactions in Aqueous Media Catalyzed by Monomeric Vanadate Species in an Apatite Framework
  作者：Takayoshi Hara、Satoko Kanai、Kohsuke Mori、Tomoo Mizugaki、Kohki Ebitani、Koichiro Jitsukawa、Kiyotomi Kaneda

  DOI：10.1021/jo0614745

  日期：2006.9.1

  reactions such as Michael and aldol reactions in aqueous media and the H−D exchange reactions using deuterium oxide. For example, a 200-mmol-scale Michael reaction under triphasic conditions proceeded rapidly, with an extremely high turnover number of up to 260 400 and an excellent turnover frequency of 48 s-1. No vanadium leaching was detected during the above reactions, and the catalyst was readily recycled

  甲钒酸钙磷灰石（VAP），其中PO 4 3 -羟基磷灰石（HAP），钙10（PO 4）6（OH）2，完全被取代的VO 4 3 -在磷灰石框架，被合成。VAp的理化分析表明存在分离出的VO 4具有五价氧化态的四面体单元。VAp可作为高性能异质碱催化剂，用于各种碳-碳键形成反应，例如水性介质中的迈克尔和醛醇反应以及使用氘化氢的H-D交换反应。例如，三相条件下的200毫摩尔规模迈克尔反应快速进行，具有高达260 400的非常高的转换数和第48号第一个极好的转换频率- 1。在上述反应过程中未检测到钒的浸出，并且催化剂易于循环使用而没有活性损失。
• A New Method for the Preparation of Michael Adducts and Cyclic Enones Using Lithium Chloride-Hexamethylphosphoramide System.
  作者：Yutaka OZAKI、Ayako KUBO、Kyouko OKAMURA、Sang-Won KIM

  DOI：10.1248/cpb.43.734

  日期：——

  A new procedure using lithium chloride in hexamethylphosphoramide was found to be useful for the synthesis of Michael-type adducts and cyclic enones. Selectivity for the two products could be controlled by altering the reaction temperature employed. The urea-type solvents were also examined instead of hexamethylphosphoramide.

  一种使用氯化锂和六甲基磷酰胺的新程序被发现对迈克尔型加成物和环己烯酮的合成非常有用。通过改变反应温度，可以控制两种产品的选择性。此外，还研究了以脲类溶剂替代六甲基磷酰胺的情况。
• Monomeric Metal Aqua Complexes in the Interlayer Space of Montmorillonites as Strong Lewis Acid Catalysts for Heterogeneous Carbon-Carbon Bond-Forming Reactions
  作者：Tomonori Kawabata、Masaki Kato、Tomoo Mizugaki、Kohki Ebitani、Kiyotomi Kaneda

  DOI：10.1002/chem.200400672

  日期：2005.1

  scandium catalysts (Cu(2+)- and Sc(3+)-monts) were easily prepared by treating Na(+)-mont with the aqueous solution of the copper nitrate and scandium triflate, respectively. The resulting Cu(2+)- and Sc(3+)-monts showed outstanding catalytic activities for a variety of carbon-carbon bond-forming reactions, such as the Michael reaction, the Sakurai-Hosomi allylation, and the Diels-Alder reaction, under

  蒙脱土包裹的铜和scan催化剂（Cu（2 +）-和Sc（3 +）-monts）可以通过分别用硝酸铜和三氟甲磺酸scan的水溶液处理Na（+）-mont来轻松制备。所得的Cu（2 +）-和Sc（3 +）-monts对各种碳-碳键形成反应（例如Michael反应，Sakurai-Hosomi烯丙基化和Diels-Alder反应）表现出出色的催化活性在无溶剂或水性条件下使用。蒙特催化剂的显着活性归因于能够稳定金属阳离子的带负电荷的硅酸盐层。此外，这些催化剂可重复使用，而活性和选择性没有任何明显的损失。Cu（2 +）-mont催化的Michael反应通过三元复合物进行，其中1和2
• Creation of monomeric La complexes on apatite surfaces and their application as heterogeneous catalysts for Michael reactions
  作者：Kohsuke Mori、Michitaka Oshiba、Takayoshi Hara、Tomoo Mizugaki、Kohki Ebitani、Kiyotomi Kaneda

  DOI：10.1039/b512030f

  日期：——

  Using a cation-exchange method, an equimolar substitution of La3+ for Ca2+ occurred by the treatment of stoichiometric hydroxyapatite (HAP: Ca10(PO4)6(OH)2) with an aqueous solution of La(OTf)3, affording a monomeric hydroxyapatite-bound La complex (LaHAP). Physicochemical characterization by means of XRD, XPS, IR, and La K-edge XAFS analyses proved that a monomeric La3+ phosphate complex was generated on its surface. Such monomeric La3+ species function as an efficient heterogeneous catalyst for the Michael reaction of 1,3-dicarbonyls with enones under aqueous or solvent-free conditions. The work-up procedure is straightforward and the spent catalyst could be recycled without any loss of the catalytic activity. Further application to an asymmetric version was also investigated using various apatite catalysts modified with chiral organic ligands. Enantioselectivity was found to depend on the chiral ligand, solvent, and rare earth metal triflate precursor (RE(OTf)3) for the reaction of methyl 1-oxoindan-2-carboxylate with methyl vinyl ketone. Under optimized reaction conditions, a monomeric fluoroapatite-bound La complex catalyst modified with (R,R)-tartaric acid (TA-LaFAP) provided the Michael adduct quantitatively in up to 60% ee.

  采用阳离子交换法，通过将化学计量的羟基磷灰石（HAP：Ca\(}_10}\)(PO\(}_4}\))\(}_6}\)(OH)\(}_2}\)）与La(OTf)\(}_3}\)的水溶液处理，实现了La\(}^3+}\)对Ca\(}^2+}\)的等摩尔取代，得到了单体羟基磷灰石结合的镧配合物（LaHAP）。通过XRD、XPS、IR和La K边XAFS分析的物理化学表征证明，在其表面生成了单体La\(}^3+}\)磷酸盐配合物。这种单体La\(}^3+}\)物种作为高效的非均相催化剂，在水相或无溶剂条件下对1,3-二羰基化合物与烯酮的迈克尔加成反应具有催化作用。后处理过程简单，且催化剂可回收，无催化活性损失。此外，还研究了通过各种含手性有机配体的磷灰石催化剂的进一步应用，以实现不对称版本。在甲基1-氧茚-2-羧酸酯与甲基乙烯基酮的反应中，产物的对映选择性取决于手性配体、溶剂和稀土金属三氟甲磺酸盐前体（RE(OTf)\(}_3}\)）。在优化的反应条件下，经过(R,R)-酒石酸（TA-LaFAP）修饰的单体氟磷灰石结合的镧配合物催化剂，能使迈克尔加成产物达到定量收率，最高对映体过量值达60%。
• Supported phenolates as efficient catalysts of the Michael reaction
  作者：Duncan J Macquarrie

  DOI：10.1016/s0040-4039(98)00672-8

  日期：1998.6

  Simple, heterogeneous base catalysts based on supported phenolates can be easily prepared and are very active and selective in the Michael reaction. (C) 1998 Elsevier Science Ltd. All rights reserved.