cis-8,8-dimethylbicyclo<4.3.0>nonan-7-one | 138783-72-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-8,8-dimethylbicyclo<4.3.0>nonan-7-one
• 英文别名: cis-2,2-dimethyl-1H-octahydroinden-1-one；(3aR,7aR)-2,2-dimethyl-3a,4,5,6,7,7a-hexahydro-3H-inden-1-one
• CAS: 138783-72-9
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: JAOTWZAKERPAEI-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.79
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  8,8-dimethylbicyclo<4.3.0>non-1(6)-en-7-one 在 四丙基高钌酸铵 、 N-morpholino-N-oxide 、 氨 、 lithium 、 叔丁醇 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 cis-8,8-dimethylbicyclo<4.3.0>nonan-7-one
  参考文献：
  名称：

  13C 磁共振研究。144. 双环 [3.3.1]- 和 [3.2.2]nonan-2-one 系统中 β-烯醇化的研究

  摘要：

  虽然 3,3-二甲基双环 [3.3.1]nonan-2-one (5) 在强碱性条件 (t-BuO−/t-BuOH/185 °C) 下稳定，但其异构体 3,3-二甲基双环 [3.2 .2]nonan-2-one (6)，慢慢转化为 5。同样，3,3-二甲基双环-[3.2.2]non-6-en-2-one (8b) 重排为 [3.3.1 ] 异构体，但后者不稳定。3,3-二甲基双环[3.3.1]non-6-en-2-one (7) 的实验表明，它被转化为五种化合物，其中没有一种是 8b。主要产物 8,8-二甲基双环 [4.3.0]non-1(6),-en-7-one (11) 产生于 β-烯醇重排。Enone 11 缓慢还原为顺式和反式 8,8-二甲基双环 [4.3.0]nonan-7-one，大概是通过单电子转移。单独使用 11 的实验表明 7 → 11 的 β-烯醇重排是单向的。Haller-Bauer

  DOI：

  10.1139/v93-146

文献信息

• Acyl radicals: intermolecular and intramolecular alkene addition reactions
  作者：Dale L. Boger、Robert J. Mathvink

  DOI：10.1021/jo00031a021

  日期：1992.2

  A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed. Primary alkyl-, vinyl-, and aryl-substituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction. Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally greater-than-or-equal-to 1 x 10(6) s-1 with some occurring at rates greater-than-or-equal-to 3 x 10(7) s-1. Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical reaction conditions. Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.
• ¹³C magnetic resonance studies. 144. An examination of β-enolization in the bicyclo[3.3.1]- and [3.2.2]nonan-2-one system
  作者：David J. Muir、J.B. Stothers

  DOI：10.1139/v93-146

  日期：1993.8.1

  While 3,3-dimethylbicyclo[3.3.1]nonan-2-one (5) is stable under strongly basic conditions (t-BuO−/t-BuOH/185 °C), its isomer, 3,3-dimethylbicyclo[3.2.2]nonan-2-one (6), is slowly transformed to 5. Similarly, 3,3-dimethylbicyclo-[3.2.2]non-6-en-2-one (8b) rearranges to a [3.3.1] isomer but the latter is not stable. Experiments with 3,3-dimethylbicyclo[3.3.1]non-6-en-2-one (7) revealed that it is converted

  虽然 3,3-二甲基双环 [3.3.1]nonan-2-one (5) 在强碱性条件 (t-BuO−/t-BuOH/185 °C) 下稳定，但其异构体 3,3-二甲基双环 [3.2 .2]nonan-2-one (6)，慢慢转化为 5。同样，3,3-二甲基双环-[3.2.2]non-6-en-2-one (8b) 重排为 [3.3.1 ] 异构体，但后者不稳定。3,3-二甲基双环[3.3.1]non-6-en-2-one (7) 的实验表明，它被转化为五种化合物，其中没有一种是 8b。主要产物 8,8-二甲基双环 [4.3.0]non-1(6),-en-7-one (11) 产生于 β-烯醇重排。Enone 11 缓慢还原为顺式和反式 8,8-二甲基双环 [4.3.0]nonan-7-one，大概是通过单电子转移。单独使用 11 的实验表明 7 → 11 的 β-烯醇重排是单向的。Haller-Bauer