Bicyclo<1.1.0>butyl-1-carbinyl 3,5-dinitrobenzoate | 151508-47-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Bicyclo<1.1.0>butyl-1-carbinyl 3,5-dinitrobenzoate
• 英文别名: 1-bicyclo[1.1.0]butanylmethyl 3,5-dinitrobenzoate
• CAS: 151508-47-3
• 化学式: C₁₂H₁₀N₂O₆
• 分子量: 278.221
• InChiKey: BANHBAVAXQJKQK-UHFFFAOYSA-N

物化性质

• 沸点：
  419.4±25.0 °C(predicted)
• 密度：
  1.600±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.07
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  112.58
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Bicyclo<1.1.0>butyl-1-carbinyl 3,5-dinitrobenzoate 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 Bicyclo<1.1.0>butyl-1-carbinyl azide
  参考文献：
  名称：

  Mechanism of the solvolysis of bicyclo[1.1.1]pent-1-yl derivatives

  摘要：

  The ionization of bicyclo[1.1.1]pentyl-1 derivatives is shown to involve rearrangement to the bicyclo[1.1.0]butyl-1-carbinyl cation rather than the 3-methylenecyclobutyl cation. This is in good accord with MP2-6-31G* theoretical predictions and is in contrast to the products of solvolysis which are 3-methylenecyclobutyl derivatives.

  DOI：

  10.1021/jo00073a014
• 作为产物：
  描述：

  Bicyclo<1.1.0>butyl-1-carbinol 、 3,5-二硝基苯甲酰氯 在 叔丁基邻苯二酚 、 甲基锂 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以75%的产率得到Bicyclo<1.1.0>butyl-1-carbinyl 3,5-dinitrobenzoate
  参考文献：
  名称：

  Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations

  摘要：

  The ionization of l-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicycle[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and can be directly observed by NMR in SO2CIF. Although the major products of solvolysis of the halides are 3-methylenecyclobutyl derivatives, the corresponding cation was calculated to have a significantly higher energy than the bicyclobutylcarbinyl ion. Therefore, the products are probably formed by an attack of the nucleophile on the latter ion, accompanied by bond migration. The bridgehead iodide reacts under solvolytic conditions with azide ion to form bicyclo[1.1.0]butyl-l azide as a product. It also reacts with potassium hydroxide to give [1.1.1]propellane, and the same reaction occurs on dissolving in acetonitrile or pyridine. The reaction of 1,3-diiodobicyclo[1.1.1]pentane with ethoxide ion also was found to give [1.1.1]propellane via a nucleophilic attack on one of the iodines. The propellane reacts with methyl hypoiodite to give 3-iodobicyclo[1.1.1]pentyl-l cation, which can react with methanol to give 3-methoxybicyclo[1.1.1]pentyl-l iodide and with azide ion to give 3-iodobicyclo[1.1.1]pentyl-1 azide. These data provide evidence for a discrete 3-iodobicyclo[1.1.1]pentyl-l cation intermediate. The effect of substituents on the rate of solvolysis of bicyclo[1.1.1]pentyl-l iodide was studied. With 3-aryl substituents, a value of rho = -1.7 was found, which is similar to that observed in the solvolysis of 3-arylcyclobutyl tosylates (rho = -1.6). The 3-substituted bicyclopentyl halides usually form the corresponding 3-methylenecyclobutyl cations rather than bicyclo[1.1.0]butyl-1-carbinyl ions, because most substituents will help stabilize the former type of ion.

  DOI：

  10.1021/ja00105a046