6,6-dimethylbicyclo<3.1.1>heptan-2α-ol | 28664-08-6

• 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: 6,6-dimethylbicyclo<3.1.1>heptan-2α-ol
• 英文别名: α-nopinol；β-Nopinol；2-endo-Hydroxy-6,6-dimethylbicyclo<3.1.1>heptan；(1R,2S,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-ol
• CAS: 28664-08-6；31147-63-4；31147-64-5；51703-63-0；70223-29-9；70223-30-2；74984-18-2；74984-19-3
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: DEDZBEBBIUTZAJ-FXQIFTODSA-N

物化性质

• 沸点：
  199.1±8.0 °C(Predicted)
• 密度：
  0.997±0.06 g/cm3(Predicted)
• LogP：
  2.269 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 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

安全信息

• 海关编码：
  2906199090

反应信息

• 作为反应物：
  描述：

  2,4-二硝基苯甲酰氯 、 6,6-dimethylbicyclo<3.1.1>heptan-2α-ol 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以79%的产率得到β-nopinyl 2,4-dinitrobenzoate
  参考文献：
  名称：

  涉及应变碳-碳键的超共轭。酯和醚衍生物的结构分析以及α-和β-壬基酚的一键13 C – 13 C耦合常数

  摘要：

  σ C-C -σ* C-O涉及α-和β-nopinol，和它们的酯和醚衍生物的应变碳-碳键的相互作用已在固态使用可变氧探头被证明。这些超共轭相互作用表现为C-OR键距离对OR取代基的电子需求的强烈响应。尽管对供体CC键距离的影响不够大，无法通过X射线晶体学测量，但它们的确对13 C- 13产生了系统且可测量的影响C单键耦合常数。对于施主CC键，随着OR的电子需求增加，耦合常数降低，与该键的弱化相一致，而中间CC键耦合常数则与键增强相符，其增加。

  DOI：

  10.1021/jo3020243
• 作为产物：
  描述：

  6,6-dimethylbicyclo<3.1.1>heptan-2β-ol 在 aluminum isopropoxide 作用下， 以 异丙醇 、 丙酮 为溶剂， 反应 96.0h， 以51%的产率得到6,6-dimethylbicyclo<3.1.1>heptan-2α-ol
  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

• Solvent Shifts of Methyl Proton Resonances of Pinanols and Related Compounds
  作者：Toshifumi Hirata

  DOI：10.1246/bcsj.45.3169

  日期：1972.10

  shifts of methyl protons of a number of bicyclo[3.1.1]heptanols and their acetates were measured on carbon tetrachloride and benzene in order to examine the correlation between the benzene-induced shifts and the spatial arrangements of the functional groups concerned. Thus, the shifts induced by benzene were found to be useful in establishing both the location and the stereochemistry of methyl protons

  在四氯化碳和苯上测量了许多双环 [3.1.1] 庚醇及其乙酸酯的甲基质子的化学位移，以检查苯引起的位移与相关官能团的空间排列之间的相关性。因此，发现苯引起的位移可用于确定位于蒎烷骨架中羟基或乙酰氧基官能团附近的甲基质子的位置和立体化学。
• Acceleration of the reduction of aldehydes and ketones using Mn(dpm)3 catalyst and phenylsilane in the presence of dioxygen
  作者：Philip Magnus、Mark R Fielding

  DOI：10.1016/s0040-4039(01)01304-1

  日期：2001.9

  Saturated ketones and aldehydes are reduced to alcohols by phenylsilane and Mn(dpm)(3)(cat) in the presence of dioxygen. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Baretta,A.J. et al., Bulletin de la Societe Chimique de France, 1970, p. 3985 - 3995
  作者：Baretta,A.J. et al.

  DOI：——

  日期：——
• The Reaction of Singlet Oxygen with ?- and ?-Pinenes
  作者：Charles W. Jefford、Andr� F. Boschung、Robert M. Moriarty、Christian G. Rimbault、Mostyn H. Laffer

  DOI：10.1002/hlca.19730560748

  日期：1973.11.7

  AbstractThe reaction of photogenerated singlet oxygen with α‐ and β‐pinenes has been carefully re‐examined. α‐Pinene almost exclusively (99.3% yield) furnishes trans‐3‐hydroperoxy‐pin2(10)‐ene. However, detectable amounts of the three other possible products are also found, viz., cis‐3‐hydroperoxypin‐2 (10)‐ene (˜0.8%), and cis‐ and trans‐2‐hydroperoxypin‐3 (4)‐ene (˜0.04%). β‐Pinene gives 99.9% of 10‐hydroperoxypin‐2 (3)‐ene and a trace (˜0.01%) of norpinan‐2‐one. Rates of reaction and product composition are treated by modal analysis and reflect the operation of steric and stereoelectronic factors in a reactant‐like transition state.
• Neighboring Carbon and Hydrogen. XVIII. Solvolysis of the Nopinyl p-Bromobenzenesulfonates
  作者：S. Winstein、N. J. Holness

  DOI：10.1021/ja01616a038

  日期：1955.6