6,6-dimethyl-4-methoxybicyclo<2.2.2>octan-2-one | 122313-95-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,6-dimethyl-4-methoxybicyclo<2.2.2>octan-2-one
• 英文别名: 4-Methoxy-6,6-dimethylbicyclo[2.2.2]octan-2-one
• CAS: 122313-95-5
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: YAOCIMQKULSVOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  6,6-dimethyl-4-hydroxybicyclo<2.2.2>octan-2-one 在 吡啶 、 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 5.3h， 生成 6,6-dimethyl-4-methoxybicyclo<2.2.2>octan-2-one
  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

• Unexpectedly facile solvolysis of 3-oxobicyclo[2.2.2]oct-1-yl triflates: through-bond interaction of the .beta.-carbonyl lone pair with the cationic p orbital
  作者：Kenichi Takeuchi、Masayasu Yoshida

  DOI：10.1021/jo00277a006

  日期：1989.8
• TAKEUCHI, KENICHI;YOSHIDA, MASAYASU, J. ORG. CHEM., 54,(1989) N6, C. 3772-3773
  作者：TAKEUCHI, KENICHI、YOSHIDA, MASAYASU

  DOI：——

  日期：——
• 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.