5-methylenespiro<3.5>nonane-5-one | 132591-62-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 5-methylenespiro<3.5>nonane-5-one
• 英文别名: 5-Methylenespiro<3.5>nonane；5-methylenespiro<3,5>nonane；5-Methylenespiro[3.5]nonane；9-methylidenespiro[3.5]nonane
• CAS: 132591-62-9
• 化学式: C₁₀H₁₆
• 分子量: 136.237
• InChiKey: OBBGKUHYUUOXII-UHFFFAOYSA-N

物化性质

• 沸点：
  190.0±7.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5-methylenespiro<3.5>nonane-5-one 在 ruthenium trichloride 、 sodium periodate 、 银 、 锌 作用下， 以 四氯化碳 、 乙醚 、 乙腈 为溶剂， 反应 80.0h， 生成 dispiro<2.0.3.4>undecane-11-one
  参考文献：
  名称：

  合成和二螺重排[2.0.3.4] - ，dispiro- [3.0.3.3] -和二螺[2.1.3.3]十一烷-优选的C 4 -C 5对C 3 -C 4和C 4 -C 3对C 5 -C 6重新排列

  摘要：

  双螺环烷10 – 12已通过酸处理合成并重排。对于10，初始C 3 -C 4环扩大导致[3.3.3]丙炔21，对于11，初始C 4 -C 3环收缩导致戊烯37，而对于12，初始C 4 -C 5取决于所使用的试剂，环扩大会导致42、43、44或45。的结构43已经由3,5-二硝基苯甲酸酯的晶体结构分析来确定从中衍生出46种。将10点重排成二螺环烷47作为（±）-苯二酚48的潜在前体。

  DOI：

  10.1016/s0040-4020(01)85700-8
• 作为产物：
  描述：

  螺<3.4>辛烷-5-酮 在 盐酸 作用下， 以 乙醚 、 乙醇 、 乙腈 为溶剂， 反应 38.08h， 生成 5-methylenespiro<3.5>nonane-5-one
  参考文献：
  名称：

  合成和二螺重排[2.0.3.4] - ，dispiro- [3.0.3.3] -和二螺[2.1.3.3]十一烷-优选的C 4 -C 5对C 3 -C 4和C 4 -C 3对C 5 -C 6重新排列

  摘要：

  双螺环烷10 – 12已通过酸处理合成并重排。对于10，初始C 3 -C 4环扩大导致[3.3.3]丙炔21，对于11，初始C 4 -C 3环收缩导致戊烯37，而对于12，初始C 4 -C 5取决于所使用的试剂，环扩大会导致42、43、44或45。的结构43已经由3,5-二硝基苯甲酸酯的晶体结构分析来确定从中衍生出46种。将10点重排成二螺环烷47作为（±）-苯二酚48的潜在前体。

  DOI：

  10.1016/s0040-4020(01)85700-8

文献信息

• The magnesium complexes of 1,2-dimethylenecycloalkanes: a new method for a one-step spiroannelation
  作者：Heping Xiong、Reuben D. Rieke

  DOI：10.1016/s0040-4039(00)92361-x

  日期：1991.9

  Reactions of new dienemagnesium reagents prepared from highly reactive magnesium and 1,2-dimethylenecycloalkanes with 1,n-dibromoalkanes and bromoalkylnitriles provide a one-step method for the synthesis of commonly encountered spirocyclic systems.
• One-step spiroannulation using 1,2-bis(methylene)cycloalkane-magnesium reagents
  作者：Reuben D. Rieke、Heping Xiong

  DOI：10.1021/jo00050a036

  日期：1992.11

  A one-step method for the synthesis of a wide variety of spirocyclic systems has been developed based on the reactions of bis-electrophiles with a series of new 1,3-diene-magnesium reagents, the magnesium complexes of 1,2-bis(methylene)cycloalkanes. The direct metalation of 1,2-bis(methylene)cycloalkanes with highly reactive magnesium in THF at ambient temperature generates the corresponding diene-magnesium reagents in high yields. Reactions of the diene-magnesium reagents with 1,n-dibromoalkanes produce a large number of spirocarbocycles containing an exocyclic double bond. The ring sizes of the accessible spiro compounds can be any combinations of four- to seven-membered rings. In most cases, the initially alkylated intermediates can be trapped by protonation, giving the corresponding bromo olefins. Significantly, treatment of the diene-magnesium reagents with bromoalkyl nitriles leads to a one-step synthesis of keto-functionalized spirocycles. The initial adduct is believed to be a Grignard reagent containing a cyano group. When a bromo nitrile containing a cyclic moiety is used as the bis-electrophile, the approach provides a direct access to dispiroenones.
• Cleavage vs. rearrangement ratios and secondary deuterium kinetic isotope effects in the thermolysis of conformationally fixed cisoid vinylcyclobutanes
  作者：J. J. Gajewski、G. C. Paul

  DOI：10.1021/jo00006a006

  日期：1991.3

  The first-order rate constants for the thermally induced retro 2 + 2 cleavage and rearrangement of 5-methylenespiro[3.5]nonane occur in a 1:2 ratio. In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes. Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted. For the rearrangement of 5-methylenespiro[3.4]octane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (k(H)/k(D)2) is 1.086 +/- 0.023. This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate. The secondary KIE for cleavage of 5-methylenespiro[3.4]octane is 1.025 +/- 0.027.
• Synthesis and rearrangement of dispiro[2.0.3.4]-, dispiro-[3.0.3.3]- and dispiro[2.1.3.3]undecanes - preferred C4-C5 over C3-C4 and C4-C3 over C5-C6 rearrangements
  作者：Lutz Fitjer、Beate Rissom、Andreas Kanschik、Ernst Egert

  DOI：10.1016/s0040-4020(01)85700-8

  日期：1994.1

  10–12 have been synthesized and rearranged by treatment with acids. With 10, an initial C3-C4 ring enlargement leads to [3.3.3]propellane 21, with 11, an initial C4-C3 ring contraction leads to pentalene 37, and with 12, an initial C4-C5 ring enlargement leads to 42, 43, 44 or 45, depending on the reagent used. The structure of 43 has been determined by crystal structure analysis of the 3,5-dinitrobenzoate

  双螺环烷10 – 12已通过酸处理合成并重排。对于10，初始C 3 -C 4环扩大导致[3.3.3]丙炔21，对于11，初始C 4 -C 3环收缩导致戊烯37，而对于12，初始C 4 -C 5取决于所使用的试剂，环扩大会导致42、43、44或45。的结构43已经由3,5-二硝基苯甲酸酯的晶体结构分析来确定从中衍生出46种。将10点重排成二螺环烷47作为（±）-苯二酚48的潜在前体。