Trifluoro-methanesulfonic acid 2-oxo-bicyclo[3.2.2]non-1-yl ester | 116759-94-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: Trifluoro-methanesulfonic acid 2-oxo-bicyclo[3.2.2]non-1-yl ester
• 英文别名: (2-Oxo-1-bicyclo[3.2.2]nonanyl) trifluoromethanesulfonate
• CAS: 116759-94-5
• 化学式: C₁₀H₁₃F₃O₄S
• 分子量: 286.272
• InChiKey: FZKRRLBTLPGQHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Trifluoro-methanesulfonic acid 2-oxo-bicyclo[3.2.2]non-1-yl ester 在 吡啶 、 2,6-二甲基吡啶 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 24.0h， 生成 Trifluoro-methanesulfonic acid 2-oxo-bicyclo[3.2.1]oct-1-ylmethyl ester
  参考文献：
  名称：

  Solvolyses of 2-Oxo Bridgehead Compounds:  A Critical Examination of π-Conjugative Stabilization of α-Carbonyl Carbocations

  摘要：

  The methodology of changing ring flexibility to detect the pi-conjugative stabilization of bridgehead carbocations has been applied to eight 2-oxo (X = O) bridgehead carbocations. On the basis of the solvolytic behavior observed in kinetics and product analyses, the eight 2-oxo bridgehead substrates were classified into three categories: three substrates solvolyzing without ion-pair return that leads to primary isomers (class A), three substrates that form primary isomers by ion-pair return during solvolysis (class B), and two substrates that undergo solvent addition to the carbonyl group to form hemiacetals during solvolysis (class C). It was concluded that the substrates of class C could not be used for the present purpose. Essentially constant ethanolysis rate ratios, k(X = O)/k(X = H-2), of 10(-8.2)-10(-8.7) at 25 degrees C were obtained between four 2-oxo substrates in classes A and B and the corresponding parent unsubstituted ones. The result was interpreted to suggest that the pi-conjugative stabilization of tertiary alpha-carbonyl carbocations is negligibly small, if present. Slightly more negative k(X = O)/k(X = H-2) values of 10(-9.7) and 10(-9.2) for highly flexible bicyclo[4.2.2]dec-1-yl and bicyclo[4.3.1]dec-l-yl systems, respectively, were attributed to complex conformations in the ground and incipient carbocations. PM3 calculations on some 2-methylene and 2-oxo bridgehead carbocations supported the experimental results. Comparison of the solvolysis rates of 1,1,3,3-tetramethyl-2-oxobutyl mesylate with those of 1,1,3,3-tetramethylbutyl mesylate estimated from the rates of the corresponding chloride also failed to support the pi-conjugative stabilization of alpha-carbonyl carbocations.

  DOI：

  10.1021/jo970454n
• 作为产物：
  描述：

  三氟甲磺酸酐 、 1-hydroxybicyclo[3.2.2]nonan-2-one 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以64%的产率得到Trifluoro-methanesulfonic acid 2-oxo-bicyclo[3.2.2]non-1-yl ester
  参考文献：
  名称：

  Solvolyses of 2-Oxo Bridgehead Compounds:  A Critical Examination of π-Conjugative Stabilization of α-Carbonyl Carbocations

  摘要：

  The methodology of changing ring flexibility to detect the pi-conjugative stabilization of bridgehead carbocations has been applied to eight 2-oxo (X = O) bridgehead carbocations. On the basis of the solvolytic behavior observed in kinetics and product analyses, the eight 2-oxo bridgehead substrates were classified into three categories: three substrates solvolyzing without ion-pair return that leads to primary isomers (class A), three substrates that form primary isomers by ion-pair return during solvolysis (class B), and two substrates that undergo solvent addition to the carbonyl group to form hemiacetals during solvolysis (class C). It was concluded that the substrates of class C could not be used for the present purpose. Essentially constant ethanolysis rate ratios, k(X = O)/k(X = H-2), of 10(-8.2)-10(-8.7) at 25 degrees C were obtained between four 2-oxo substrates in classes A and B and the corresponding parent unsubstituted ones. The result was interpreted to suggest that the pi-conjugative stabilization of tertiary alpha-carbonyl carbocations is negligibly small, if present. Slightly more negative k(X = O)/k(X = H-2) values of 10(-9.7) and 10(-9.2) for highly flexible bicyclo[4.2.2]dec-1-yl and bicyclo[4.3.1]dec-l-yl systems, respectively, were attributed to complex conformations in the ground and incipient carbocations. PM3 calculations on some 2-methylene and 2-oxo bridgehead carbocations supported the experimental results. Comparison of the solvolysis rates of 1,1,3,3-tetramethyl-2-oxobutyl mesylate with those of 1,1,3,3-tetramethylbutyl mesylate estimated from the rates of the corresponding chloride also failed to support the pi-conjugative stabilization of alpha-carbonyl carbocations.

  DOI：

  10.1021/jo970454n