2-methyl-3-(2-propenyl)cyclohexanone | 129025-65-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-3-(2-propenyl)cyclohexanone
• 英文别名: 2-Methyl-5-prop-2-enylcyclohexan-1-one；2-methyl-5-prop-2-enylcyclohexan-1-one
• CAS: 129025-65-6
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: SSJVXEBTZYRGIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-3-(2-propenyl)cyclohexanone 在 对甲苯磺酸 对甲苯磺酸 作用下， 以 二氯甲烷 、 乙二醇 、 苯 为溶剂， 生成 1-methyl-6-[(tetrahydro-2H-pyran-2-yl)oxy]bicyclo[2.2.2]octan-2-one
  参考文献：
  名称：

  1,3,3-三甲基双环[2.2.2] octan-2,6-dione的新制备方法，它是（+）-Norpatchoulenol总合成中从未分离出的中间体。（±）-异-去甲七叶烯醇的正式全合成

  摘要：

  1,3,3-三甲基双环[2.2.2] octan-2,6-dione（3）的一种新制备方法以及分离和光谱表征，这是迄今为止在Liu - Ralitsch（+）合成中难以捉摸的关键中间体描述了-去甲七叶烯醇（（+）- 1a）。3的制备也构成了（±）-异-去甲酚（（±）-1b）的正式全合成，因为3与Monti和同事的中间体有关（±）-1b。

  DOI：

  10.1002/hlca.200490191
• 作为产物：
  描述：

  6-methylcyclohex-2-en-1-one 、 3-氯丙烯 在 barium 作用下， 生成 1-Allyl-6-methyl-cyclohex-2-enol 、 2-methyl-3-(2-propenyl)cyclohexanone
  参考文献：
  名称：

  Allylbarium Reagents: Unprecedented Regio- and Stereoselective Allylation Reactions of Carbonyl Compounds

  摘要：

  The first direct preparation of allylbarium reagents by reaction of insitu generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 degrees C. All reactions resulted in high yields with remarkable alpha-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)beta,gamma-unsaturated carboxylic acids were easily prepared in good yields by highly alpha-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with alpha,beta-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 degrees C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me(2)C=CHCH2Br, (C5H11CHO)-C-n, and CH3COCl).

  DOI：

  10.1021/ja00093a010

文献信息

• Allylbarium Reagents: Unprecedented Regio- and Stereoselective Allylation Reactions of Carbonyl Compounds
  作者：Akira Yanagisawa、Shigeki Habaue、Katsutaka Yasue、Hisashi Yamamoto

  DOI：10.1021/ja00093a010

  日期：1994.7

  The first direct preparation of allylbarium reagents by reaction of insitu generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 degrees C. All reactions resulted in high yields with remarkable alpha-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)beta,gamma-unsaturated carboxylic acids were easily prepared in good yields by highly alpha-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with alpha,beta-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 degrees C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me(2)C=CHCH2Br, (C5H11CHO)-C-n, and CH3COCl).
• A New Preparation of 1,3,3-Trimethylbicyclo[2.2.2]octan-2,6-dione, a Never Isolated Intermediate in a Total Synthesis of (+)-Norpatchoulenol. Formal Total Synthesis of (±)-Iso-Norpatchoulenol
  作者：Angela La Bella、Francesca Leonelli、Ilse De Salve、Luisa M. Migneco、Rinaldo Marini Bettolo

  DOI：10.1002/hlca.200490191

  日期：2004.8

  A new preparation and the isolation and spectroscopic characterization of 1,3,3-trimethylbicyclo[2.2.2]octan-2,6-dione (3), a so far elusive key intermediate in the Liu–Ralitsch total synthesis of (+)-norpatchoulenol ((+)-1a), is described. The preparation of 3 constitutes also a formal total synthesis of (±)-iso-norpatchoulenol ((±)-1b), since 3 is correlated to an intermediate in the Monti and co-workers

  1,3,3-三甲基双环[2.2.2] octan-2,6-dione（3）的一种新制备方法以及分离和光谱表征，这是迄今为止在Liu - Ralitsch（+）合成中难以捉摸的关键中间体描述了-去甲七叶烯醇（（+）- 1a）。3的制备也构成了（±）-异-去甲酚（（±）-1b）的正式全合成，因为3与Monti和同事的中间体有关（±）-1b。