2-(4-diazo-3-oxobutyl)cyclohexanone | 60719-17-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(4-diazo-3-oxobutyl)cyclohexanone
• 英文别名: 1-Diazo-4-(2-oxocyclohexyl)-2-butanon；1-Diazonio-4-(2-oxocyclohexyl)but-1-en-2-olate；2-(4-diazo-3-oxobutyl)cyclohexan-1-one
• CAS: 60719-17-7
• 化学式: C₁₀H₁₄N₂O₂
• 分子量: 194.233
• InChiKey: NBYJUIMBWSDJAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  36.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-diazo-3-oxobutyl)cyclohexanone 在 tin(ll) chloride 作用下， 以 二氯甲烷 为溶剂， 以51%的产率得到bicyclo[5.3.0]decane-2,10-dione
  参考文献：
  名称：

  Synthesis of 1,3-diketones using .alpha.-diazo ketones and aldehydes in the presence of tin(II) chloride

  摘要：

  DOI：

  10.1021/jo00305a029
• 作为产物：
  描述：

  2-环己酮甲酸乙酯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 氯甲酸异丁酯 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 为溶剂， 反应 3.5h， 生成 2-(4-diazo-3-oxobutyl)cyclohexanone
  参考文献：
  名称：

  α-重氮-β-羟基酮的重排以合成双环[ m]。n .1]烷酮

  摘要：

  铑催化的稠合双环α-重氮-β-羟基酮的分解可产生桥联双环[ m]的良好收率。n .1]酮通过重排途径。

  DOI：

  10.1021/acs.orglett.7b01963

文献信息

• 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。
• A New and Mild Heterogeneous Catalytic Decomposition of α-Diazo Carbonyl Compounds Using Montmorillonite or Zeolite
  作者：Sengodagounder Muthusamy、Srinivasarao Arulananda Babu、Chidambaram Gunanathan、Raksh Vir Jasra

  DOI：10.1055/s-2002-20452

  日期：——

  A very mild method of decomposition of various α-diazo carbonyl compounds 1 in the presence of environmentally attractive solid acids such as montmorillonite K-10 or zeolite H-Y in a heterogeneous manner to furnish α-hydroxy/alkoxy ketones in very good yield is reported. Interestingly, novel bicycloalkane-1,3-diones and 3-furanones were obtained as unusual products in the case of aliphatic/alicyclic α-diazo carbonyl compounds.

  报告采用一种非常温和的方法，在对环境有吸引力的固体酸（如蒙脱石 K-10 或沸石 H-Y）存在下，以异构方式分解各种δ-重氮羰基化合物 1，从而以非常好的收率得到δ-羟基/烷氧基酮。有趣的是，在脂肪族/脂环族 δ-重氮羰基化合物中，作为不常见的产物，获得了新型双环烷-1,3-二酮和 3-呋喃酮。
• Synthetic scope of the triethyloxonium ion catalyzed homologation of ketones with diazoacetic esters
  作者：William L. Mock、Marvis E. Hartman

  DOI：10.1021/jo00423a015

  日期：1977.2
• Amberlyst-15 mediated decomposition of α-diazo carbonyl compounds
  作者：Sengodagounder Muthusamy、Srinivasarao Arulananda Babu、Chidambaram Gunanathan、Raksh Vir Jasra

  DOI：10.1016/s0040-4039(01)00936-4

  日期：2001.7

  An efficient heterogeneous catalytic method for the synthesis of alpha -hydroxy ketones from alpha -diazo carbonyl compounds 1, 3 and 6 in the presence of Amberlyst-15. a macro reticular ion exchange resin, is reported. The desired products were obtained at room temperature or by ultrasonication in good yield. Interestingly, novel fused 3-furanones and bicycloalkane-1,3-diones were obtained as unusual products in the case of alicyclic alpha -diazo carbonyl compounds. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation
  作者：Albert Padwa、Richard L. Chinn、Susan F. Hornbuckle、Zhijia J. Zhang

  DOI：10.1021/jo00010a019

  日期：1991.5

  The carbenoid intermediate derived by the treatment of several 1-diazobutanediones with rhodium(II) acetate undergoes ready transannular cyclization onto the neighboring keto group to give five-membered ring carbonyl ylides. The dipole derived from ethyl 4-diazo-2-methyl-3-oxobutyrate was found to undergo a rapid proton transfer, producing 5-ethoxy-4-methyl-3-(2H)-furanone. When the position adjacent to the diazo carbonyl group is blocked with two substituent groups, however, smooth 1,3-dipolar cycloaddition occurs. The observed regioselectivity can be nicely accommodated in terms of frontier molecular orbital (FMO) theory. A type II FMO interaction is involved since carbonyl ylides possess one of the smallest HOMO-LUMO energy gaps of common 1,3-dipoles. The rhodium(II)-catalyzed reaction of 1-diazo-6-phenyl-2,6-hexanedione afforded a mixture of products. In addition to the expected cycloadduct, a product derived from the bimolecular addition of the rhodium carbenoid to benzene was obtained. The formation of a mixture of products in this case suggests that entropic factors have sufficiently retarded the rate of intramolecular cyclization so as to allow the bimolecular reaction with benzene to occur. No observable cycloadduct was obtained from the diazohexanedione system, thereby indicating that the longer tether was sufficient to shut down dipole formation.