7,7-dimethylbicyclo[2.2.1]heptane-1-carbonyl chloride | 5271-65-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 7,7-dimethylbicyclo[2.2.1]heptane-1-carbonyl chloride
• CAS: 5271-65-8
• 化学式: C₁₀H₁₅ClO
• 分子量: 186.681
• InChiKey: IOLQTPNQKZROHP-UHFFFAOYSA-N

物化性质

• 沸点：
  212.4±9.0 °C(Predicted)
• 密度：
  1.134±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2916209090

反应信息

• 作为反应物：
  描述：

  7,7-dimethylbicyclo[2.2.1]heptane-1-carbonyl chloride 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 二硫化碳 、 乙醚 为溶剂， 生成 7,7-Dimethyl-1-(α-hydroxy-4-methoxy-benzyl)-bicyclo<2.2.1>heptan
  参考文献：
  名称：

  Carbonium Ions. IX. Monoarylalkyl Cations^1,2

  摘要：

  The electronic absorption spectra and the chemical and thermodynamic stabilities of monoarylalkyl cations have been examined a function of cation structure.

  DOI：

  10.1021/ja01502a066
• 作为产物：
  描述：

  酮基蒎酸 在 吡啶 、 sodium hydroxide 、 氯化亚砜 、 肼 作用下， 以 乙二醇 为溶剂， 反应 2.0h， 生成 7,7-dimethylbicyclo[2.2.1]heptane-1-carbonyl chloride
  参考文献：
  名称：

  Carbonium Ions. IX. Monoarylalkyl Cations^1,2

  摘要：

  The electronic absorption spectra and the chemical and thermodynamic stabilities of monoarylalkyl cations have been examined a function of cation structure.

  DOI：

  10.1021/ja01502a066

文献信息

• The elimination of carbon monoxide from acid derivatives. Part III. Planar carbonium ions as necessary intermediates
  作者：David G. Pratt、Eugene Rothstein

  DOI：10.1039/j39680002548

  日期：——

  Elimination of carbon monoxide from acid chlorides by the Friedel-Crafts reaction is precluded if the resulting carbonium ions are restricted to non-planar geometry by bicyclic or other structures with a rigid molecular framework. In such cases the normal ketones are obtained.

  如果所得的碳离子被具有刚性分子骨架的双环或其他结构限制为非平面几何形状，则无法通过Friedel-Crafts反应从酰氯中消除一氧化碳。在这种情况下，可获得正常的酮。
• Reactions of Triphenyltin Hydride with Certain Acid Chlorides and Carboxylic Acids
  作者：Eugene J. Kupchik、Robert J. Kiesel

  DOI：10.1021/jo01340a025

  日期：1966.2
• Solvolyses of 2-Oxo Bridgehead Compounds:  A Critical Examination of π-Conjugative Stabilization of α-Carbonyl Carbocations
  作者：Ken'ichi Takeuchi、Yasushi Ohga、Masayasu Yoshida、Keizo Ikai、Tadashi Shibata、Midori Kato、Akio Tsugeno

  DOI：10.1021/jo970454n

  日期：1997.8.1

  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.