2,2-五亚甲基环己酮 | 1781-83-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,2-五亚甲基环己酮
• 中文别名: 螺[5.5]十一烷-1-酮
• 英文名称: spiro[5.5]undecan-1-one
• 英文别名: Spiro<5.5>undecan-1-one；spiro<5.4>decan-1-one；2,2-pentamethylenecyclohexanone；Spiro[5.5]undecan-1-on；Spiro<5.5>undecen-2-on-7；1-Oxo-spiro<5.5>undecan；spiro[5.5]undecan-5-one
• CAS: 1781-83-5
• 化学式: C₁₁H₁₈O
• mdl: MFCD00019474
• 分子量: 166.263
• InChiKey: ISUXBNXLVOPNBA-UHFFFAOYSA-N

物化性质

• 熔点：
  39.0-39.6 °C
• 沸点：
  103 °C(Press: 8.5 Torr)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.909
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2914299000

反应信息

• 作为反应物：
  描述：

  2,2-五亚甲基环己酮 在 2,2,2-tribromo-1,3,2-benzodioxaphosphole 作用下， 以88%的产率得到1-溴螺[5.5]十一碳-1-烯
  参考文献：
  名称：

  锆配合轴承η 5 -5”，6' ，7'- trihydrospiro [环烷烃-1,4'-茚]配体

  摘要：

  通过相应的γ-二酮的碱催化环化或通过酸催化的相应二乙烯基酮的纳扎罗夫环化成功地合成了包括螺-环戊基和-环己基片段的四氢茚。这些取代的环戊二烯用正丁基锂金属化。锂盐与Cp * ZrCl 3的以下反应产生了三个带有螺环烷烃片段的新型锆茂。一这些配合物，（η 5 -5'，6'，7'- trihydrospiro [环己烷-1,4' - （2-甲基茚基）]）（η 5 -五甲基环戊二烯基）二氯化锆，已通过X射线晶体结构分析。

  DOI：

  10.1016/j.jorganchem.2010.04.021
• 作为产物：
  描述：

  环己甲酸甲酯 在 tris(dibenzoylmethano)iron(III) samarium diiodide 、 sodium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 丙酮 为溶剂， 反应 16.25h， 生成 2,2-五亚甲基环己酮
  参考文献：
  名称：

  Intramolecular nucleophilic acyl substitution reactions of halo-substituted esters and lactones. New applications of organosamarium reagents

  摘要：

  Intramolecular nucleophilic acyl substitution reactions involving a broad range of halo substituted carboxylic acid derivatives have been accomplished in excellent yield employing samarium(II) iodide as the reductive coupling agent. Although particular substrates cyclized most effectively in THF in the presence of tripiperidinophosphine oxide, carboxylic acid esters, the focus of this report, cyclize equally well without such an additive in the presence of a catalytic quantity of iron(III) complexes. Thus a comprehensive series of halo substituted esters were cyclized in excellent yield to the corresponding 4-, 5-, and 6-membered carbocycles. The reaction is extremely mild and selective as demonstrated by experiments wherein alkyl chlorides, acetals, and olefins remain completely intact under the reaction conditions. In addition to introducing a convenient procedure for preparing stereodefined spirocyclic systems, a new ring expansion sequence has been developed that appears extremely general for the preparation of various ring systems.

  DOI：

  10.1021/jo00077a053

文献信息

• The photochemical or thermal rearrangement of oxaziranes as a method in alkaloid synthesis
  作者：Martin E. Kuehne、W.H. Parsons

  DOI：10.1016/s0040-4020(01)88617-8

  日期：1983.1

  The conversion of cyclic ketones to β-arylethyl amine derived imines, their oxidation to oxaziranes and subsequent photochemical rearrangement to N-(β-arylethyl) lactams was probed as a potential method for alkaloid syntheses.

  探讨了将环酮转化为β-芳基乙胺衍生的亚胺，将其氧化为恶唑烷，然后将其光化学重排为N-（β-芳基乙基）内酰胺，作为生物碱合成的潜在方法。
• Palladium-Catalyzed Intramolecular Hydroalkylation of Alkenyl- ?-Keto Esters, ?-Aryl Ketones, and Alkyl Ketones in the Presence of Me3SiCl or HCl
  作者：Xiaoqing Han、Xiang Wang、Tao Pei、Ross A. Widenhoefer

  DOI：10.1002/chem.200400459

  日期：2004.12.17

  palladium-catalyzed hydroalkylation, but rather served as a source of HCl, which presumably catalyzes enolization of the ketone. Identification of HCl as the active promoter of palladium-catalyzed hydroalkylation led to the development of an effective protocol for the hydroalkylation of alkyl 3-butenyl ketones that employed sub-stoichiometric amounts of 2, HCl, and CuCl2 in a sealed tube at 70 degrees C.

  3-丁烯基β-酮酸酯或3-丁烯基α-芳基酮与催化量的[PdCl2（CH3CN）2]（2）和化学计量的Me3SiCl或Me3SiCl / CuCl2在二恶烷中的反应温度为25-70摄氏度以高产率和高区域选择性生成2-取代的环己酮。该方案容许许多酯和芳基，并容许在烯丙基，烯醇，顺式和反式末端烯烃位置上的取代。原位NMR实验表明，氯硅烷并不直接参与钯催化的加氢烷基化反应，而是用作HCl的来源，推测是催化酮的烯醇化反应。
• SPIRO COMPOUNDS AND PHARMACEUTICAL USE THEREOF
  申请人：Shimada Takashi

  公开号：US20090170908A1

  公开（公告）日：2009-07-02

  The Spiro compound represented by the following general formula [Ia], its pharmaceutically acceptable salt or a solvate thereof

  以下是用中文翻译的结果：由下列通用式[Ia]表示的螺环化合物，其药用可接受盐或其溶剂化合物
• Anhydrous ferric chloride dispersed on silica gel induced ring enlargement of tertiary cycloalkanols. II : a convenient homologation of cycloalkanones, preparation of spiro systems and propella -γ-lactones
  作者：A. Fadel、J. Salaun

  DOI：10.1016/s0040-4020(01)96528-7

  日期：1985.1

  The reagent obtained by mixing anhydrous FeCl3 and silica gel induced, in the lack of any solvent, dehydration of tertiary cycloalkanols, specific C4→C5 and C5 →C6 enlargement, formation of spiro compounds and propella-γ- lactones and cleavage of tetrahydropyranyl ethers.

  通过在无溶剂的情况下将无水FeCl 3和硅胶混合得到的试剂，导致叔环链烷醇脱水，C 4 →C 5和C 5 →C 6增大，形成螺环化合物和螺旋桨-γ-内酯，四氢吡喃基醚的裂解。
• Stereospecific Construction of Contiguous Quaternary All-Carbon Centers by Oxidative Ring Contraction
  作者：Xin Yu、Jiadong Hu、Zhigao Shen、Hui Zhang、Jin-Ming Gao、Weiqing Xie

  DOI：10.1002/anie.201609975

  日期：2017.1.2

  ketones was facilitated by the action of H2O2 under operationally simple and environmentally benign reaction conditions. The process was highly regioselective and enables stereospecific construction of contiguous quaternary all‐carbon centers from stereodefined all‐substituted all‐cyclic ketones. The asymmetric syntheses of (+)‐cuparene and (+)‐tochuinyl acetate were also successively achieved by taking advantage

  在操作简单和环境友好的反应条件下，H 2 O 2的作用促进了环状α-甲酰基酮的氧化环收缩。该过程具有高度的区域选择性，并能够从立体定义的全取代的全环酮立体构筑连续的季碳全碳中心。利用该新方案还成功实现了（+）-cuparene和（+）-tochuinyl乙酸酯的不对称合成。