Bicyclo<1.1.0>butyl-1-carbinol | 4935-02-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Bicyclo<1.1.0>butyl-1-carbinol
• 英文别名: Bicyclo<1.1.0>butan-1-methanol；Bicyclo[1.1.0]butan-1-methanol；Bicyclo[1.1.0]butan-1-ylmethanol；1-bicyclo[1.1.0]butanylmethanol
• CAS: 4935-02-8
• 化学式: C₅H₈O
• 分子量: 84.1179
• InChiKey: QGFJQJCTRJWABB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Bicyclo<1.1.0>butyl-1-carbinol 在 sodium azide 、 叔丁基邻苯二酚 、 甲基锂 作用下， 以 乙醚 、 N,N-二甲基甲酰胺-d7 为溶剂， 反应 99.0h， 生成 Bicyclo<1.1.0>butyl-1-carbinyl azide
  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
• 作为产物：
  描述：

  3-(苄氧基)环丁烷羧酸甲酯 在 钯 lithium aluminium tetrahydride 、 对叔丁基邻苯二酚 、 氢气 、 sodium hydride 作用下， 以 甲醇 、 乙醚 为溶剂， 生成 Bicyclo<1.1.0>butyl-1-carbinol
  参考文献：
  名称：

  双环[1.1.0]丁烷

  摘要：

  综述了双环[1.1.0]丁烷及其某些衍生物的化学性质。讨论了键角变形对其应变能，轨道杂交及其反应性的影响。

  DOI：

  10.1016/s0040-4020(01)98361-9

文献信息

• Mechanism of the solvolysis of bicyclo[1.1.1]pent-1-yl derivatives
  作者：Kenneth B. Wiberg、Neil McMurdie

  DOI：10.1021/jo00073a014

  日期：1993.10

  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.
• Bicyclo[1.1.0]butane
  作者：K.B. Wiberg、G.M. Lampman、R.P. Ciula、D.S. Connor、P. Schertler、J. Lavanish

  DOI：10.1016/s0040-4020(01)98361-9

  日期：1965.1

  The chemistry of bicyclo[1.1.0]butane and some of its derivatives is reviewed. The effect of its bond angle deformation on its strain energy, its orbital hybridization, and its reactivity is discussed.

  综述了双环[1.1.0]丁烷及其某些衍生物的化学性质。讨论了键角变形对其应变能，轨道杂交及其反应性的影响。
• Formation and Reactions of Bicyclo[1.1.1]pentyl-1 Cations
  作者：Kenneth B. Wiberg、Neil McMurdie

  DOI：10.1021/ja00105a046

  日期：1994.12

  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.