tricyclo<4.2.1.0^3,7>nonan-3-ol | 111457-85-3

• 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: tricyclo<4.2.1.0^3,7>nonan-3-ol
• 英文别名: 1,5-Methanopentalen-1(2H)-ol, hexahydro-；tricyclo[4.2.1.03,7]nonan-3-ol
• CAS: 111457-85-3
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: VCEPCSVFFOPLEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• 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

• 作为产物：
  描述：

  甲醇 、 spiro(bicyclo<2.2.1>heptane-2,1'-cyclopropan)-exo-6-ol 在 硫酸 作用下， 反应 24.0h， 以67%的产率得到3-methoxytricyclo<4.2.1.0^3,7>nonane
  参考文献：
  名称：

  Ion-Molecule Complexes in 1,2-Alkyl Shifts

  摘要：

  The internal return of neutral leaving groups was studied in rearrangements of polycyclic systems (2-norpinyl --> 2-norbornyl, endo- --> exo-tricyclo[5.2.1.0(2,6)]dec-8-yl, bicyclo[3.2.0]hept-2-yl --> 7-norbornyl, and 4-protoadamantyl --> 2-adamantyl). Acid catalysis was applied to O-18-labeled alcohols in aqueous organic solvents, to alcohols in methanol, and to ethers R-O-R' in alcohols R''-OH. The leaving group was found to attack the migration origin in competition with solvent molecules, Return:exchange ratios were obtained from product distributions, either directly or by kinetic simulation (in cases of partial exchange prior to rearrangement). If departure and return of the leaving group occur on the same side of the carbon framework, return:exchange ratios ranging from 1 to 11.5 were observed. Less internal return was found for bridged than for open carbocations, Migration of the departing molecule to the opposite face (exo reversible arrow endo) or to a beta carbon is a minor process (return:exchange 0.1), in accordance with previous reports on inverting displacements and allylic 1,3 shifts. These data are rationalized in terms of short-lived ion-molecule (ion-dipole) complexes whose collapse competes with ligand exchange.

  DOI：

  10.1021/ja00154a010

文献信息

• Ion-Molecule Complexes in 1,2-Alkyl Shifts
  作者：Andrea Gappa、Ekkehard Herpers、Roland Herrmann、Volker Huelsewede、Wilhelm Kappert、Matthias Klar、Wolfgang Kirmse

  DOI：10.1021/ja00154a010

  日期：1995.12

  The internal return of neutral leaving groups was studied in rearrangements of polycyclic systems (2-norpinyl --> 2-norbornyl, endo- --> exo-tricyclo[5.2.1.0(2,6)]dec-8-yl, bicyclo[3.2.0]hept-2-yl --> 7-norbornyl, and 4-protoadamantyl --> 2-adamantyl). Acid catalysis was applied to O-18-labeled alcohols in aqueous organic solvents, to alcohols in methanol, and to ethers R-O-R' in alcohols R''-OH. The leaving group was found to attack the migration origin in competition with solvent molecules, Return:exchange ratios were obtained from product distributions, either directly or by kinetic simulation (in cases of partial exchange prior to rearrangement). If departure and return of the leaving group occur on the same side of the carbon framework, return:exchange ratios ranging from 1 to 11.5 were observed. Less internal return was found for bridged than for open carbocations, Migration of the departing molecule to the opposite face (exo reversible arrow endo) or to a beta carbon is a minor process (return:exchange 0.1), in accordance with previous reports on inverting displacements and allylic 1,3 shifts. These data are rationalized in terms of short-lived ion-molecule (ion-dipole) complexes whose collapse competes with ligand exchange.