1-Methylenspiro<4.5>decan-2-on | 111689-29-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Methylenspiro<4.5>decan-2-on
• 英文别名: 1-methylenespiro[4.5]decan-2-one；1-Methylidenespiro[4.5]decan-2-one；4-methylidenespiro[4.5]decan-3-one
• CAS: 111689-29-3
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: CUUYFDGXVSJPOZ-UHFFFAOYSA-N

物化性质

• 沸点：
  273.6±10.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  螺[3.5]壬烷-3-酮 在 manganese triacetate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 15.0h， 生成 1-Methylenspiro<4.5>decan-2-on
  参考文献：
  名称：

  Manganese(III)-based oxidative fragmentation-cyclization reactions of unsaturated cyclobutanols

  摘要：

  Allylic cyclobutanols 1, 10, 21, 27, 32, 39, 51, and 58 are oxidatively fragmented by Mn(OAc)3.2H2O in EtOH to give tertiary radicals as shown in eq 1. These tertiary radicals undergo both 6-endocyclization to the alpha,beta--unsaturated ketone to afford a-keto radicals and 5-exo-cyclization to provide beta-keto cyclopentylmethyl radicals. The a-keto radicals produced by 6-endo-cyclization are reduced to ketones or dimerize. The beta-keto radicals formed by 5-exo-cyclization are oxidized by Cu(OAc)2 to yield methylenecyclopentanones and rearrange to give 3-oxocyclohexyl radicals that are oxidized by Cu(OAC)2 to afford cyclohexenones. Acetylenic cyclobutanols 47, 49, and 65 are oxidatively fragmented by Mn(OAC)3.2H2O in EtOH to provide tertiary radicals that cyclize to give alpha-keto vinyl radicals, which abstract a hydrogen atom to yield methylenecyclopentanones. Pentenylcyclobutanol 75 is oxidatively fragmented by Mn(OAc)3.2H2O to afford tertiary radical 74, which cyclizes to furnish cyclopentylmethyl radicals 77 and 78, which are oxidized by Cu(OAC)2 to methylenecyclopentanes 76 and 79.

  DOI：

  10.1021/jo00077a054

文献信息

• Nazarov Cyclization of 4-Cycloalkylidene-5-(trimethylsilyl)pent-1-en-3-one Derivatives. Synthesis of Spiro[4.5]decane, Spiro[4.4]nonane, and Their Derivatives
  作者：Chiaki Kuroda、Hiroyuki Koshio、Akira Koito、Hiroshi Sumiya、Atsushi Murase、Yukari Hirono

  DOI：10.1016/s0040-4020(00)00589-5

  日期：2000.8

  Spiro[4.5]decane and spiro[4.4]nonane ring systems were synthesized by FeCl3-induced Nazarov cyclization of α-(trimethylsilylmethyl)divinyl ketone derivatives. It was found that the double bond position of the product is controlled by the presence/absence of α′-substituent, while trimethylsilyl group is essential to obtain the products in good yields. Spiro[4.4]nonanes having exo-methylene group underwent

  通过FeCl 3诱导的α-（三甲基甲硅烷基甲基）二乙烯基酮衍生物的纳扎罗夫环化反应合成了螺[4.5]癸烷和螺[4.4]壬烷环系统。发现产物的双键位置受α'-取代基的存在/不存在的控制，而三甲基甲硅烷基对于以高收率获得产物是必不可少的。具有外亚甲基的螺[4.4]壬烷进行了重排，形成双环[4.3.0]壬烷。
• Synthesis of spiro[4.5]decane ring system through allylsilane promoted spiroannulation
  作者：Chiaki Kuroda、Yukari Hirono

  DOI：10.1016/0040-4039(94)85034-8

  日期：1994.9

  Spiro[4.5]decane ring system with methylene ketone on five membered ring was synthesized by Nazarov cyclization of α-(trimethylsilylmethyl)divinyl ketone derivatives.

  通过Nazarov环合α-（三甲基甲硅烷基甲基）二乙烯基酮衍生物的纳扎罗夫，合成了在五元环上带有亚甲基酮的螺[4.5]癸烷环系。
• Eilbracht, Peter; Acker, Michael; Haedrich, Ines, Chemische Berichte, 1988, vol. 121, p. 519 - 524
  作者：Eilbracht, Peter、Acker, Michael、Haedrich, Ines

  DOI：——

  日期：——
• Kuroda Chiaki, Hirono Yukari, Tetrahedron Lett, 35 (1994) N 37, S 6895-6896
  作者：Kuroda Chiaki, Hirono Yukari

  DOI：——

  日期：——