endo-2-methoxybicyclo<2.2.1>heptane | 10395-53-6

• 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: endo-2-methoxybicyclo<2.2.1>heptane
• 英文别名: 2-methoxybicyclo<2.2.1>heptane；endo-norbornyl methyl ether；endo-2-methoxynorbornane；endo-2-norborneol；endo-5-Methoxy-bicyclo<2.2.1>heptan；endo-2-Norbornyl-methylaether；(1R,2S,4S)-2-methoxybicyclo[2.2.1]heptane
• CAS: 10395-53-6；10395-55-8；60263-60-7
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: WMYWLMCIILHCPB-RNJXMRFFSA-N

物化性质

• 沸点：
  158.6±8.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 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：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  endo-2-methoxybicyclo<2.2.1>heptane 在 HOF* CH₃CN 、 sodium fluoride 作用下， 以 氯仿 、 水 、 乙腈 为溶剂， 以80%的产率得到降樟脑
  参考文献：
  名称：

  Oxidative Cleavage of Methyl Ethers Using the HOF.cntdot.CH3CN Complex

  摘要：

  HOF . CH3CN complex, made easily by bubbling fluorine diluted with nitrogen through aqueous acetonitrile, proved to be a suitable oxidizer for various methyl ethers. Secondary ethers are oxidized to ketones and even to lactones via Baeyer-Villiger type of oxidation. The reaction is ionic, and the reagent's electrophilic oxygen attacks the relatively electron rich C-H bend alpha to the ether moiety. It was found that the more sterically hindered is the C-H bond in question, the slower the reaction. In cases where this bond is an electron poor one as in benzoin methyl ether (9), no reaction takes place. When labeled (HOF)-O-18 . CH3CN is used on a O-16 methyl ether, the resulting ketone possesses only the heavier oxygen isotope. Primary methyl ethers are somewhat slower to react, but they too were oxidized in very good yields to acids via the corresponding aldehydes.

  DOI：

  10.1021/jo00130a029
• 作为产物：
  描述：

  spiro(bicyclo<2.2.1>heptane-2,3'-diazirine) 生成 endo-2-methoxybicyclo<2.2.1>heptane
  参考文献：
  名称：

  Kirmse Wolfgang, Meinert Thomas, Modarelli David A., Platz Matthew S., J. Amer. Chem. Soc, 115 (1993) N 20, S 8918-8927

  摘要：

  DOI：

文献信息

• Catalysis by solid super acids. 20. Nafion-H catalyzed reductive cleavage of acetals and ketals to ethers with triethylsilane
  作者：George A. Olah、Takehiko Yamato、Pradeep S. Iyer、G. K. Surya Prakash

  DOI：10.1021/jo00364a044

  日期：1986.7
• Arnold, Donald R.; Snow, Miles S., Canadian Journal of Chemistry, 1988, vol. 66, p. 3012 - 3026
  作者：Arnold, Donald R.、Snow, Miles S.

  DOI：——

  日期：——
• Enhancement of Reaction Efficiency by Functionalized Alcohols on Gold(I)-Catalyzed Intermolecular Hydroalkoxylation of Unactivated Olefins
  作者：Toshifumi Hirai、Akiyuki Hamasaki、Aki Nakamura、Makoto Tokunaga

  DOI：10.1021/ol9023166

  日期：2009.12.3

  Intermolecular hydroalkoxylation of unactivated olefins catalyzed by the combination of gold(I) and electron deficient phosphine ligands has been developed. Although pairings of unactivated olefins and common aliphatic alcohols gave unsatisfactory results In gold catalyzed hydroalkoxylations, the use of alcohol substrates bearing coordination functionalities such as halogen or alkoxy groups showed great improvement of reactivity.
• Kirmse, Wolfgang; Siegfried, Rainer; Wroblowsky, Heinz-Juergen, Chemische Berichte, 1983, vol. 116, # 5, p. 1880 - 1896
  作者：Kirmse, Wolfgang、Siegfried, Rainer、Wroblowsky, Heinz-Juergen

  DOI：——

  日期：——
• 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.