(1'E,2RS,6SR)-2,6-dimethyl-2-(3'-oxobut-1'-enyl)cyclohexanone | 131228-09-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1'E,2RS,6SR)-2,6-dimethyl-2-(3'-oxobut-1'-enyl)cyclohexanone
• 英文别名: (2R,6S)-2,6-dimethyl-2-[(E)-3-oxobut-1-enyl]cyclohexan-1-one
• CAS: 131228-09-6；131321-13-6；131321-14-7；131321-15-8
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: RIDGNSRIGLCNGH-QSLLUVDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  二甲基环已酮 、 (E)-4-chloro-3-buten-2-one 、 lithium diisopropyl amide 生成 (1'E,2RS,6SR)-2,6-dimethyl-2-(3'-oxobut-1'-enyl)cyclohexanone
  参考文献：
  名称：

  DANCER, ROBERT J.;, HAYNES RICHARD K.;LOUGHLIN, WENDY A.;VONWILLER, SIMON+, AUSTRAL. J. CHEM., 43,(1990) N, C. 1375-1389

  摘要：

  DOI：

文献信息

• Efficient Trapping of Ketone Enolates With Acrylate and β-Sulfonylacrylate Thioesters, β-Sulfonyl-, β-Sulfinyl- and β-Chloro-Vinyl Ketones; Facile Preparation of a Hydrindanone, cis-Dimethyloctalone, and Unsaturated 1,5-Dicarbonyl Compounds
  作者：RJ Dancer、RK Haynes、WA Loughlin、SC Vonwiller

  DOI：10.1071/ch9901375

  日期：——

  Tandem conjugate addition-ring closure involving reaction of the lithium enolate arising from conjugate addition of lithiated (E)-but-2- enyldiphenylphosphine oxide to 2-methyl-cyclopent-2-enone with two moles of t-butylthioacrylate generates a hydrindanol, and, in the presence of copper(I), a lactone derived from the hydrindanol. β-Sulfonylacrylate phenyl and t-butyl thioesters, β-chlorovinyl, β- sulfonyl- and β-sulfinyl-vinyl ketones react with the foregoing enolate, and with the enolate generated through conjugate addition of a methylcuprate to 2-methylcyclohexenone to give unsaturated 1,5-dicarbonyl compounds. The β-chlorovinyl ketones in particular react rapidly and in high yield. 2-Methylcyclohexenone has thereby been converted into a cis-dimethyl octalone; the conversion illustrates the effectiveness of β-chlorovinyl methyl ketone in the Robinson annelation. Reactions of the lithium enolate and titanium enol of 2,6- dimethylcyclohexanone with the β-substituted enones to give the corresponding unsaturated 1,5-dicarbonyl compounds and other products are also recorded.

  串联共轭加成-环闭合反应涉及将锂化的(E)-2-丁烯基二苯氧化膦与 2-甲基-2-环戊烯酮共轭加成而生成的烯酸锂与两摩尔的硫代丙烯酸叔丁酯反应，生成氢茚醇，并在铜(I)存在下生成氢茚醇衍生的内酯。β-磺酰基丙烯酸酯苯基和 t-丁基硫代酯、β-氯乙烯基、β-磺酰基和 β-磺酰基乙烯基酮与上述烯醇发生反应，并与 2-甲基环己烯酮与甲基缩二脲共轭加成生成的烯醇发生反应，生成不饱和的 1,5-二羰基化合物。其中，β-氯乙烯酮的反应速度快，产率高。2-Methylcyclohexenone 由此转化为顺式二甲基辛酮；这一转化说明了 β-氯乙烯基甲基酮在罗宾逊环化反应中的有效性。此外，还记录了 2,6-二甲基环己酮的锂烯醇和钛烯醇与 β-取代烯酮的反应，从而得到相应的不饱和 1,5-二羰基化合物和其他产物。