4-hydroxybicyclo<2.2.2>octan-2-one | 66348-59-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxybicyclo<2.2.2>octan-2-one
• 英文别名: 4-Hydroxy-bicyclo<2.2.2>octanon；4-Hydroxybicyclo[2.2.2]octan-2-one
• CAS: 66348-59-2
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: WTHUKYWLYDGUGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-hydroxybicyclo<2.2.2>octan-2-one 在 吡啶 作用下， 以 二氯甲烷 、 二甲基亚砜 、 乙腈 为溶剂， 反应 9.0h， 生成 3-methylenebicyclo<2.2.2>oct-1-yl triflate
  参考文献：
  名称：

  Solvolyses of 3-oxo- and 3-methylenebicyclo[2.2.2]oct-1-yl triflates: through-bond interaction of a .beta.-carbonyl lone pair with a cationic p orbital

  摘要：

  The rates of solvolysis of 3,3-dimethyl-2-oxobicyclo[2.2.2]oct-1-yl triflate (1b), 2-methylenebicyclo[2.2.2]oct-1-yl-triflate (2b), 5,5-dimethyl-3-oxobicyclo[2.2.2]oct-1-yl triflate (3b), 3-oxobicyclo[2.2.2]oct-1-yl triflate (4b), 3-methylenebicyclo[2.2.2]oct-1-yl triflate (5b), 3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate (6b), and bicyclo[2.2.2]oct-1-yl triflate (7b) have been determined in 80% ethanol at 25-degrees-C. The O-18- and deuterium-labeling studies exclude both carbonyl addition and the enolization processes in the solvolyses of 3b and 4b. The rate ratios 1b/6b and 2b/7b are 10(-9.1) and 10(-3.9), respectively, indicating that the oxo substituent at the C(2) position is more electron withdrawing than the methylene substituent at the same position. In contrast, the rate ratios 3b/6b and 5b/7b, 10(-2.3) and 10(-2.2), respectively, are comparable with each other. Moreover, the rate ratio 4b/5b is 2.3, suggesting that the 3-oxo substituent is less electron withdrawing than the 3-methylene substituent with respect to the cationic center. Evaluation of the inductive effect of the oxo substituent at the C(3) position by means of the reported rates of solvolysis of various 2-or 3-substituted and unsubstituted bicyclo[2.2.2]oct-1-yl p-nitrobenzenesulfonates (14, 13, and 15, respectively) indicates a rate enhancement of 10(3)-10(4) for 3b and 4b. This marked enhancement is interpreted as evidence of the stabilization of the 3-oxo carbocation by a through-bond interaction between the beta-carbonyl lone pair and the cationic p orbital. The m Y relationships and the formation of fragmentation products 11 (9%) and 12 (20%) in the methanolyses of 3-oxo compounds 3b and 4b, respectively, support the through-bond interaction.

  DOI：

  10.1021/jo00061a036

文献信息

• Selective Reduction of Hydroxy Carbonyl to Carbonyl Compounds with Trialkylborane/Trifluoromethanesulfonic Acid
  作者：George A. Olah、An-hsiang Wu

  DOI：10.1055/s-1991-26479

  日期：——

  Triethyl- or triisopropylborane/trifluoromethanesulfonic (triflic) acid is a convenient reagent for the selective reduction of hydroxy substituted carboxylic acids, ketones and aldehydes to yield the corresponding carbonyl compounds. The scope of the reaction, experimental conditions and suggested mechanism are discussed.

  三乙硼或三异丙硼/三氟甲磺酸（三氟磺酸）是一种方便的选择性还原羟基取代羧酸、酮和醛的试剂，能够生成相应的羰基化合物。本文讨论了该反应的适用范围、实验条件和建议的机理。
• Solvolyses of 3-oxo- and 3-methylenebicyclo[2.2.2]oct-1-yl triflates: through-bond interaction of a .beta.-carbonyl lone pair with a cationic p orbital
  作者：Masayasu Yoshida、Kenichi Takeuchi

  DOI：10.1021/jo00061a036

  日期：1993.4

  The rates of solvolysis of 3,3-dimethyl-2-oxobicyclo[2.2.2]oct-1-yl triflate (1b), 2-methylenebicyclo[2.2.2]oct-1-yl-triflate (2b), 5,5-dimethyl-3-oxobicyclo[2.2.2]oct-1-yl triflate (3b), 3-oxobicyclo[2.2.2]oct-1-yl triflate (4b), 3-methylenebicyclo[2.2.2]oct-1-yl triflate (5b), 3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate (6b), and bicyclo[2.2.2]oct-1-yl triflate (7b) have been determined in 80% ethanol at 25-degrees-C. The O-18- and deuterium-labeling studies exclude both carbonyl addition and the enolization processes in the solvolyses of 3b and 4b. The rate ratios 1b/6b and 2b/7b are 10(-9.1) and 10(-3.9), respectively, indicating that the oxo substituent at the C(2) position is more electron withdrawing than the methylene substituent at the same position. In contrast, the rate ratios 3b/6b and 5b/7b, 10(-2.3) and 10(-2.2), respectively, are comparable with each other. Moreover, the rate ratio 4b/5b is 2.3, suggesting that the 3-oxo substituent is less electron withdrawing than the 3-methylene substituent with respect to the cationic center. Evaluation of the inductive effect of the oxo substituent at the C(3) position by means of the reported rates of solvolysis of various 2-or 3-substituted and unsubstituted bicyclo[2.2.2]oct-1-yl p-nitrobenzenesulfonates (14, 13, and 15, respectively) indicates a rate enhancement of 10(3)-10(4) for 3b and 4b. This marked enhancement is interpreted as evidence of the stabilization of the 3-oxo carbocation by a through-bond interaction between the beta-carbonyl lone pair and the cationic p orbital. The m Y relationships and the formation of fragmentation products 11 (9%) and 12 (20%) in the methanolyses of 3-oxo compounds 3b and 4b, respectively, support the through-bond interaction.