1,1'-Cyclopentylidenbis(ethanon) | 69994-30-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1'-Cyclopentylidenbis(ethanon)
• 英文别名: 1,1-Diacetylcyclopentane；Ethanone, 1,1'-cyclopentylidenebis-；1-(1-acetylcyclopentyl)ethanone
• CAS: 69994-30-5
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: BLYOUOMTJJPCLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,1'-Cyclopentylidenbis(ethanon) 在 copper(II) bis(trifluoromethanesulfonate) 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 30.0h， 以27%的产率得到螺[4.4]壬烷-1,4-二酮
  参考文献：
  名称：

  Kobayashi, Yoshiro; Taguchi, Takeo; Morikawa, Tsutomu, Chemical and pharmaceutical bulletin, 1980, vol. 28, # 1, p. 262 - 267

  摘要：

  DOI：
• 作为产物：
  描述：

  1,4-二碘代丁烷 、 乙酰丙酮 在 N(Et)4(1+)*(2-pyrrolidone-anion) 作用下， 生成 1,1'-Cyclopentylidenbis(ethanon)
  参考文献：
  名称：

  Electroorganic chemistry. 103. Selective C-alkylation of .beta.-diketones

  摘要：

  DOI：

  10.1021/jo00239a052

文献信息

• Diastereo- and Regioselective Synthesis of Diquinanes and Related Systems from Tricyclo[3.3.0.02,4]octanes by Chemical Electron Transfer (CET)
  作者：Waldemar Adam、Thomas Heidenfelder、Coskun Sahin

  DOI：10.1055/s-1995-4072

  日期：1995.9

  A new synthetic methodology for diquinanes by one-electron oxidation of tricyclo[3.3.0.02,4]octanes and subsequent stereocontrolled rearrangement is provided. The latter compounds are conveniently accessible through acid-catalyzed isopyrazole cycloaddition, followed by hydrogenation and photoextrusion of molecular nitrogen. The oxidative rearrangement of the tricyclooctanes proceeds catalytically and cleanly to afford regio- and diastereoselectively the corresponding diquinanes.

  提供了一种通过三环[3.3.0.02,4]辛烷的单电子氧化和随后的立体控制重排合成二喹烷的新合成方法。后者化合物可通过酸催化异吡唑环加成，随后氢化和分子氮的光排出方便地获得。三环辛烷的氧化重排催化且清洁地进行，区域和立体选择性地得到相应的二喹烷。
• Convenient, High-Yield Method for the Methylation of 1,3-Diketones
  作者：Anil Choudhary、Alfons L. Baumstark

  DOI：10.1055/s-1989-27359

  日期：——

  A general method for the facile dimethylation of 1,3-diketones is presented. The method involves the use of readily available, inexpensive reagents and is carried out under mild conditions. Monomethylation may be carried out by slight modification (simplification) of the procedure. Several examples are presented which show that the method is applicable to alkylations with primary halides as well. Isolated yields for monoalkylation are approximately 95% while those for dialkylation are ≍90%. Alkylation is taking place by the reaction of the enolates of 1,3-diketones [generated in toluene by treatment with anhydrous potassium carbonate in the presence of tetraalkylammonium bromide (phase-transfer catalyst)] with alkyl halides.

  提出了一种简便的1,3-二酮的双甲基化一般方法。该方法使用易得且廉价的试剂，并在温和的条件下进行。通过对程序的轻微修改（简化），可以进行单甲基化。提供了几个示例，表明该方法同样适用于与初级卤化物的烷基化。单烷基化的分离产率约为95%，而双烷基化的产率约为90%。烷基化是通过将1,3-二酮的烯醇盐（在无水碳酸钾和四烷基铵溴化物（相转移催化剂）处理的甲苯中生成）与烷基卤化物反应实现的。
• Synthesis of Spiro[5.4]decenones and Their Transformation into Bicyclo[4.4]deca-1,4-dien-3-ones by Domino ?Elimination- Double-Wagner-Meerwein-Rearrangement? Reactions
  作者：Gopal Bose、Ehsan Ullah、Peter Langer

  DOI：10.1002/chem.200400707

  日期：2004.12.3

  The [3+3] cyclization of 1,3-bis-silyl enol ethers with 1,1-diacylcyclopentanes allows a convenient synthesis of spiro[5.4]decenones. Treatment of these compounds with trifluoroacetic acid (TFA) afforded a great variety of bicyclo[4.4.0]deca-1,4-dien-3-ones containing an angular alkyl group. This core structure occurs in a number of pharmacologically relevant natural products.

  1,3-二甲硅烷基烯醇醚与1,1-二酰基环戊烷的[3 + 3]环化反应可方便地合成螺[5.4]癸烯。用三氟乙酸（TFA）处理这些化合物可得到各种各样的带有角烷基的双环[4.4.0] deca-1,4-dien-3-one。这种核心结构出现在许多与药理有关的天然产物中。
• Imidazolium salts as phase transfer catalysts for the dialkylation and cycloalkylation of active methylene compounds
  作者：Sengodagounder Muthusamy、Boopathy Gnanaprakasam

  DOI：10.1016/j.tetlet.2004.11.141

  日期：2005.1

  The dialkylation and cycloalkylation reactions of active methylene compounds in the presence of readily available imidazolium salts (ionic liquids) as phase transfer catalysts were performed to afford the respective dialkylated or cycloalkylated products. This method is very efficient for the synthesis of 1,1-disubstituted derivatives and cyclopropane and cyclopentane ring systems in a facile manner

  在作为相转移催化剂的易得的咪唑鎓盐（离子液体）存在下，进行活性亚甲基化合物的二烷基化和环烷基化反应，得到相应的二烷基化或环烷基化产物。该方法对于以容易的方式合成1，1-二取代的衍生物以及环丙烷和环戊烷环体系非常有效。
• Perkin–Markovnikov Type Reaction Initiated with Electrogenerated Superoxide Ion
  作者：Fumihiro Ojima、Tetsuo Osa

  DOI：10.1246/bcsj.62.3187

  日期：1989.10

  The cyclic condensation of active methylene compounds such as diethyl malonate, dimethyl malonate, ethyl acetoacetate, or acetylacetone and dibromoalkanes such as 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,3-dibromobutane, or 1,4-dibromopentane with electrogenerated superoxide ion was studied electrochemically in N,N-dimethylformamide (DMF) using cyclic voltammetry (CV) and controlled potential macro-electrolysis. The CV shows that electrogenerated superoxide ion reacts with both active methylene compounds and dibromoalkanes in the dissolved oxygen medium. Controlled potential macro-electrolysis of the above components generally yielded cycloalkanes as the main products. In comparison, the chemical method using sodium ethoxide was also carried out. Two reaction mechanisms via the proton abstraction of active methylene compounds with electrogenerated superoxide ion and via the nucleophilic attack of the superoxide ion on dibromoalkanes are presented.

  活性亚甲基化合物，如二乙基马来酸酯、二甲基马来酸酯、乙酰乙酸乙酯或乙酰乙酮，与二溴烷烃，如1,2-二溴乙烷、1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,6-二溴己烷、1,3-二溴丁烷或1,4-二溴戊烷的循环缩合反应，采用循环伏安法（CV）和控制电位宏电解法在N,N-二甲基甲酰胺（DMF）中进行了电化学研究。CV结果表明，电生超氧阴离子在溶解氧介质中与活性亚甲基化合物和二溴烷烃均发生反应。上述组分的控制电位宏电解通常以环烷烃作为主要产物。相比之下，使用乙醇钠的化学方法也进行了研究。提出了两种反应机理：一种是活性亚甲基化合物与电生超氧阴离子的质子抽取反应，另一种是超氧阴离子对二溴烷烃的亲核攻击反应。