3-(2-氧代环己基)丙酸乙酯 | 4095-02-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 3-(2-氧代环己基)丙酸乙酯
• 中文别名: 乙基3-(2-羰基环己基)丙酸盐
• 英文名称: 3-(2-oxocyclohexyl)propionic acid ethyl ester
• 英文别名: ethyl 3-(2-oxocyclohexyl)propionate；Ethyl 3-(2-oxocyclohexyl)propanoate
• CAS: 4095-02-7
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: MTKILJJDTJQCBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(2-氧代环己基)丙酸乙酯 在 lithium aluminium tetrahydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 28.0h， 生成 3-(1,4-dioxaspiro[4,5]dec-6-yl)propan-1-ol
  参考文献：
  名称：

  Visible Light Initiated Photosensitized Electron Transfer Cyclizations of Aldehydes and Ketones to Tethered α,β-Unsaturated Esters:  Stereoselective Synthesis of Optically Pure C-Furanosides

  摘要：

  Photosensitized one-electron reductive activation of aldehydes/ketones tethered with activated olefins leads to efficient cyclization to give diastereoselective cycloalkanols in high yield. The activation is promoted by secondary and dark electron transfer from visible light (405 nm) initiated photosensitized electron transfer generated 9,10-dicyanoanthracene radical anion (DCA(.-)). The DCA(.-) is produced by electron transfer using either triphenylphosphine (Ph3P) as sacrificial electron donor (PS-A) or 1,5-dimethoxynaphthalene (DMN) as primary electron donor and ascorbic acid as sacrificial electron donor (PS-B), to light-absorbing DCA. The cyclization is suggested to involve ketyl radical intermediate. High trans diastereoselectivity is observed during the formation of cycloalkanols. This cyclization strategy is further extended for the stereoselective synthesis of optically pure C-furanoside (41), starting from naturally occuring L-tartaric acid. The stereochemistry of 41 is suggested based on the single-crystal X-ray diffraction data.

  DOI：

  10.1021/jo9702812
• 作为产物：
  描述：

  环己酮 以 四氢呋喃 、 甲苯 为溶剂， 反应 18.0h， 生成 3-(2-氧代环己基)丙酸乙酯
  参考文献：
  名称：

  还原吲哚制备六氢咔唑衍生物

  摘要：

  在亚胺离子中间体的阶段，通过用氢化硼酸盐试剂还原而中断了苯基肼衍生物的费歇尔吲哚化，在位置4a提供了具有官能化侧链的六氢咔唑衍生物。用于该转化的环状δ-氧代酯是从丙烯酸乙酯和环烷酮获得的。

  DOI：

  10.1002/ejoc.202001226

文献信息

• Microwave Promoted Regeneration of Carbonyl Compounds from Oximes Using N, N-Dichloro Poly(Styrene-co-divinylbenzene)Sulphonamide Resin
  作者：A.G. Beldar、Mamta Sharma

  DOI：10.1155/2011/590923

  日期：——

  An efficient, economically viable and operationally simple method was developed for deoximation of oximes (of ketones and aldehydes) to their corresponding carbonyl compounds using polymer beads ofN, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin. Polymeric reagent offered speedy conversion and substantial yields of products under mild condition and is recyclable. Deoximation was monitored by the use of¹³C NMR.

  一种高效、经济可行且操作简单的方法已经开发出来，用于将肟（酮和醛的肟）脱氧成它们相应的羰基化合物，使用聚合物珠子的N，N-二氯聚（苯乙烯-共-二乙烯苯）磺酰胺树脂。聚合物试剂在温和条件下提供了快速转化和可观的产物收率，并且可回收利用。通过使用13C NMR监测了脱氧反应。
• Construction of Fused Cyclooctanoid Ring Systems via Seven-Membered Ring Carbonyl Ylides
  作者：Sengodagounder Muthusamy、Srinivasarao Arulananda Babu、Chidambaram Gunanathan、Eringathodi Suresh、Parthasarathi Dastidar

  DOI：10.1246/bcsj.75.801

  日期：2002.4

  A series of α-diazo carbonyl compounds tethered to cyclopentanone/cyclohexanone/1-tetralone units have been synthesized using a diazomethane solution to construct various fused cyclooctane ring systems via rhodium-generated carbonyl ylides. The reaction of rhodium(II) acetate dimer with various α-diazo carbonyl compounds generated transient cyclic seven-membered ring carbonyl ylides, which underwent facile 1,3-dipolar cycloadditions with dipolarophiles, like N-phenylmaleimide, p-benzoquinone, and DMAD to furnish a variety of fused epoxy-bridged cyclooctane ring systems in a tandem manner. Interestingly, an oxepine ring system was generated via an intramolecular proton transfer of a seven-membered ring carbonyl ylide. A tri-oxa polycyclic compound was obtained in the case of p-benzoquinone as dipolarophile. A single-crystal X-ray analysis of a fused cyclootanoid derivative is reported to decisively establish the structure and stereochemistry of the fused epoxy-bridged cyclooctane ring systems; a further analysis revealed the existence of a unique intermolecular C–H···π interaction motif in the solid-state architecture.

  一系列连接到环戊酮/环己酮/1-四氢萘酮单元的α-重氮羰基化合物通过使用重氮甲烷溶液，通过铑产生的羰基叶立德构建了各种融合的环辛烷环体系。铑(II)醋酸二聚体与各种α-重氮羰基化合物的反应生成了瞬态的七元环羰基叶立德，这些叶立德与亲二极体如N-苯基马来酰亚胺、对苯醌和DMAD进行了方便的1,3-偶极环加成反应，以串联方式提供了多种融合的环氧桥接环辛烷环体系。有趣的是，通过七元环羰基叶立德的分子内质子转移生成了一个oxepine环体系。当对苯醌作为亲二极体时，得到了一个三氧杂多环化合物。报道了对融合环辛烷类衍生物的单晶X射线分析，以明确确定融合环氧桥接环辛烷环体系的结构和立体化学；进一步分析揭示了固态结构中存在的独特分子间C-H···π相互作用模式。
• Efficient Synthesis of ω-Functionalized Nonanoic Acids
  作者：L. Cotarca、P. Delogu、P. Maggioni、A. Nardelli、R. Bianchini、S. Sguassero

  DOI：10.1055/s-1997-4462

  日期：1997.3

  Starting from cyclohexanone and acrylonitrile, a four-step synthesis of the title open-chain C9 compounds is reported. An improved protocol for cyanoethylation of cyclohexanone in the presence of a catalytic amount of cyclohexylamine afforded 3-(2-oxocyclohexyl)-propanenitrile (1) in 92% yield. Cyclohexaneperoxycarboxylic acid (CHPCA) is introduced as a highly efficient reagent in the Baeyer-Villiger rearrangement of 1, yielding over 90% of 2. Pyrolysis of 2 afforded under optimized conditions 3 in 92% yield and 99% regioisomeric purity, otherwise a mixture of three unsaturated isomeric ω-cyano nonenoic acids 3, 10 and 11 is obtained. Partial hydrogenation of 3 allowed the isolation of 4 in 90% yield. Hydrogenation of 4 at elevated hydrogen pressure gave 9-aminononanoic acid (5), whereas hydrolysis of 4 led to 1,9-nonanedioic acid (azelaic acid, 6). Both, 5 and 6 are valuable C9 monomers for the preparation of polyamides with specific properties.

  从环己酮和丙烯腈出发，报道了一种四步合成标题开链C9化合物的改进方法。在催化量的环己胺存在下，对环己酮的腈乙基化反应进行了改进，以92%的产率得到3-(2-氧代环己基)-丙腈(1)。环己烷过氧羧酸(CHPCA)作为一种高效试剂被引入到1的Baeyer-Villiger重排反应中，产率超过90%。2在优化条件下进行热解，得到92%产率和99%区域异构纯度的3，否则会得到三种不饱和异构的Φ-氰基壬烯酸3、10和11的混合物。3的部分氢化反应允许分离出4，产率为90%。在较高的氢压下对4进行氢化反应得到9-氨基壬酸(5)，而4的水解反应则生成1,9-壬二酸(壬二酸，6)。5和6都是制备具有特定性能聚酰胺的有价值C9单体。
• Efficient and Scaleable Methods for ω-Functionalized Nonanoic Acids:  Development of a Novel Process for Azelaic and 9-Aminononanoic Acids (Nylon-6,9 and Nylon-9 Precursors)
  作者：Livius Cotarca、Pietro Delogu、Alfonso Nardelli、Paolo Maggioni、Roberto Bianchini、Stefano Sguassero、Stefano Alini、Roberto Dario、Giuliano Clauti、Giorgio Pitta、Gianpaolo Duse、Fabrizio Goffredi

  DOI：10.1021/op000081j

  日期：2001.1.1

  propanecarboxylic acid derivatives 1 in high yield. Cyclohexaneperoxycarboxylic acid (CHPCA) is introduced as highly efficient reagent in Baeyer−Villiger rearrangement of 1. Pyrolysis of 2 (EWG = CN) afforded under optimized conditions 3 in high yield and regioisomeric purity, otherwise a mixture of three unsaturated isomeric ω-cyano nonenoic acids is obtained. Partial hydrogenation of unsaturated acids 3 allowed

  讨论了标题为开链 C-9 化合物（用于制备具有特定性能的聚酰胺的有价值的单体）的一种新的收敛合成和方法。从相对便宜的原材料开始，例如环己酮和活化的 C-3 烯烃，该方法提供了聚合物级的 ω-官能化壬酸。在催化量的伯胺或仲胺存在下环己酮的氰乙基化或羧基乙基化的改进方案以高产率得到 3-(2-氧代-环己烷)丙烷羧酸衍生物 1。将环己烷过氧羧酸 (CHPCA) 作为高效试剂引入 1 的 Baeyer-Villiger 重排。在优化的条件 3 下以高产率和区域异构纯度提供 2 (EWG = CN) 的热解，否则得到三种不饱和异构ω-氰基壬烯酸的混合物。不饱和酸 3 的部分氢化允许分离饱和的长链双官能化酸 4。 4 的水解导致 1...
• A Novel Tandem [2 + 2] Cycloaddition−Dieckmann Condensation with Ynolate Anions. Efficient Synthesis of Substituted Cycloalkenones and Naphthalenes via Formal [<i>n</i> + 1] Cycloaddition
  作者：Mitsuru Shindo、Yusuke Sato、Kozo Shishido

  DOI：10.1021/jo015929w

  日期：2001.11.1

  A novel tandem [2 + 2] cycloaddition-Dieckmann condensation via ynolate anions is described. Ynolate anions are useful for the formation of reactive beta-lactone enolates via a pathway not involving the enolization of the corresponding beta-lactones. The [2 + 2] cycloaddition of ynolate anions with delta- or gamma-keto esters, followed by Dieckmann condensation, gives bicyclic beta-lactones, which

  描述了一种新颖的串联双[2 + 2]环加成反应-狄克曼经由via酸根阴离子的缩合反应。矢酸根阴离子可通过不涉及相应的β-内酯烯醇化的途径用于反应性β-内酯烯醇酸酯的形成。用δ-或γ-酮酸酯将[2 + 2]环酸酯阴离子进行环加成反应，然后进行Dieckmann缩合反应，生成双环β-内酯，该二环β-内酯易于脱羧生成一个合成有用的2,3-二取代的环戊烯酮和环己烯酮。该串联反应应用于高度取代的萘的新型一锅合成。

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