2-Methyl-3-<2-oxo-cyclohexyl>-propionsaeure-methylester | 63714-94-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-Methyl-3-<2-oxo-cyclohexyl>-propionsaeure-methylester
• 英文别名: Methyl 2-methyl-3-(2-oxocyclohexyl)propanoate
• CAS: 63714-94-3
• 化学式: C₁₁H₁₈O₃
• mdl: MFCD01050418
• 分子量: 198.262
• InChiKey: OTPHUJJJZNBFAV-UHFFFAOYSA-N

物化性质

• 沸点：
  276.7±13.0 °C(Predicted)
• 密度：
  1.022±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.818
• 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：

  2-Methyl-3-<2-oxo-cyclohexyl>-propionsaeure-methylester 在 氢氧化钾 、 氯甲酸乙酯 、 三乙胺 作用下， 以 乙醚 、 水 为溶剂， 反应 19.75h， 生成 2-(4-diazo-2-methyl-3-oxobutyl)cyclohexanone
  参考文献：
  名称：

  Construction of Fused Cyclooctanoid Ring Systems via Seven-Membered Ring Carbonyl Ylides

  摘要：

  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。

  DOI：

  10.1246/bcsj.75.801
• 作为产物：
  描述：

  2-(溴甲基)丙烯酸甲酯 在 magnesium 、 mercury dichloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 3.0h， 生成 2-Methyl-3-<2-oxo-cyclohexyl>-propionsaeure-methylester
  参考文献：
  名称：

  Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol

  摘要：

  The reductive cyclizations of various ketones tethered to activated olefins such as alpha,beta-unsaturated esters, nitriles, sulfoxides, and sulfides were mediated by magnesium in dry methanol in the presence of mercuric chloride. When treated with magnesium in dry methanol at -23-degrees-C all of the ketones except nitrile 9 (42%) and 5-oxa-8-keto-2-enoate 5 (13%) gave excellent yields (79-98%) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the beta-carbon of the activated olefin and the carbonyl carbon. The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst. For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups. The product isomer ratios were independent of the substrate geometry (E or Z). In contrast to the ketones, aldehydes tethered to alpha,beta-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products. When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved. Under the same reaction conditions alpha,beta-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85%) as the major product along with a small amount (9%) of cyclized product 19t. In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54%). With excess magnesium (15 equiv), however, alpha,beta-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95%) via deoxygenated sulfide 18. Both 16Z and 16E afforded product 19t as a single isomer. It is suggested that the reductive cyclization of the alpha,beta-unsaturated esters and nitriles proceed by means of nucleophilic attack of a beta-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group. The cyclization of the alpha,beta-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.

  DOI：

  10.1021/jo00085a036

文献信息

• <b>The Enamine Alkylation and Acylation of Carbonyl Compounds</b>
  作者：Gilbert. Stork、A. Brizzolara、H. Landesman、J. Szmuszkovicz、R. Terrell

  DOI：10.1021/ja00885a021

  日期：1963.1
• A NEW ALKYLATION OF CARBONYL COMPOUNDS. II¹
  作者：Gilbert Stork、Hans K. Landesman

  DOI：10.1021/ja01600a087

  日期：1956.10
• 403. The reaction of enamines with electrophilic olefins. A synthesis of cyclobutanes
  作者：Ian Fleming、John Harley-Mason

  DOI：10.1039/jr9640002165

  日期：——
• Palladium-assisted carboacylation of olefins
  作者：Louis S. Hegedus、W. H. Darlington

  DOI：10.1021/ja00535a027

  日期：1980.7
• Bicyclic lactones, perfumery uses thereof, processes for preparing same and intermediates therefor
  申请人：Weiss A. Richard

  公开号：US20070054837A1

  公开（公告）日：2007-03-08

  Described are bicyclic lactones, both fused ring lactones defined according to the generic structure: and spiro lactones defined according to the generic structure: uses thereof in augmenting, enhancing or imparting aromas in or to perfume compositions, perfumed articles, colognes and perfumed polymers; processes for preparing such bicyclic lactones and intermediates therefor.