1-methylbicyclo<2.2.1>heptan-endo-2-ol | 766-25-6

• 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: 1-methylbicyclo<2.2.1>heptan-endo-2-ol
• 英文别名: 1-methyl-endo-2-norbornanol；(+/-)-1-methyl-norbornane-2endo-ol；(+/-)-1-Methyl-norbornan-2endo-ol；endo-1-Methyl-bicyclo<2.2.1>heptan-2-ol；1-Methyl-2-endo-norbornanol；(1R,2S,4S)-1-methylbicyclo[2.2.1]heptan-2-ol
• CAS: 766-25-6；3588-21-4；16651-55-1；23351-28-2；54339-50-3；103664-34-2
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: YWRVUMNRBIOXJQ-GJMOJQLCSA-N

物化性质

• 熔点：
  76 °C
• 沸点：
  132 °C(Press: 17 Torr)
• 密度：
  1.079±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  0
• 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：

  1-methylbicyclo<2.2.1>heptan-endo-2-ol 在 水 、 硝酸 作用下， 生成 1-methyl-norbornan-2-one
  参考文献：
  名称：

  Toivonen, Suomen Kemistilehti B, 1953, vol. 26, p. 75,76

  摘要：

  DOI：
• 作为产物：
  描述：

  Bicyclo[3.1.1]heptan-2-ol, 2-methyl- 在 硫酸 作用下， 生成 1-methylbicyclo<2.2.1>heptan-endo-2-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

• Norbornanes. Part 20. Inductivity and bridging in 2-norbornyl cations
  作者：Rolf Bielmann、Francesco Fuso、Cyril A. Grob

  DOI：10.1002/hlca.19880710203

  日期：1988.3.16

  The solvolysis rates and products of several 1-substituted 2exo- and 2-endo-norbornyl p-toluenesulfonates 7 and 8, respectively, have been determined. Hydrolyses of these epimeric tosylates yielded rearranged products in varying amounts, except when the substituent was COOCH3 or CN. The logarithms of the rate constants (log k) for the endo-series 8 correlated linearly with the corresponding inductive

  分别确定了几种1-取代的2-外-和2-内-降冰片基对甲苯磺酸盐7和8的溶剂分解速率和产物。这些取代基甲苯磺酸酯的水解产生不同数量的重排产物，除非取代基为COOCH 3或CN。速率常数（日志的对数ķ）为内切-系列8相关线性地对应感应常数与反应常数σρ我的-1.24。另一方面，记录exo系列7的k个值出现以适应2次回归线，第一行（ρ我由甲苯磺酸盐的是离化定义= -1.90），其中重排，所述第三阳离子11，第二（ρ我通过甲苯磺酸酯= -1.86）7（R = H ，COOCH 3和CN）离子化为不对称桥连的次级阳离子19。这些结果证实了C（6）的与ρ的独特参与我的-2.00在2-的电离外-nor冰片甲苯磺酸酯。
• Chiral Synthesis via Organoboranes. 42. Selective Reductions. 57. Efficient Kinetic Resolution of Representative α-Tertiary Ketones with <i>B</i>-Chlorodiisopinocampheylborane
  作者：P. Veeraraghavan Ramachandran、Guang-Ming Chen、Herbert C. Brown

  DOI：10.1021/jo951206z

  日期：1996.1.1

  Kinetic resolution of racemic alpha-tertiary ketones with 0.5-0.6 molar equiv of B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric and enantiomeric excess, with the unreacted ketone recovered in very high ee. For example, ethyl 1-methyl-8-oxocyclopentane- and -cyclohexanecarboxylates are partially reduced to recover the ketone in 91 greater than or equal to 99% ee and the product alcohols in up to 94% de, with >90% ee for the major diastereomer. Bicyclic ketones, such as 1-methyl- and 1-ethylnorcamphor, camphor, and camphenilone, are readily resolved to provide the ketone in 92 to greater than or equal to 99% ee, with the product alcohol recovered in high de and ee. Dihydrospiro[bicyclo[3.2.1]octane-2,2'(3'H)-furan]-3-one is resolved to provide the ketone in greater than or equal to 99% ee and the product alcohol in greater than or equal to 99% de. In all the cases studied, the R-isomer of the ketone is recovered when (d)Ipc(2)BCl is used for kinetic resolution, while (l)Ipc(2)BCl provides the S-ketone. Optimum conditions for obtaining the product alcohol, or the ketone, or both, in very high yields and ee have been established.
• Hirsjaervi, Annales Academiae Scientiarum Fennicae, Series A2: Chemica, 1957, # 81, p. 13
  作者：Hirsjaervi

  DOI：——

  日期：——
• Chiral Synthesis via Organoboranes. 43. Selective Reductions. 58. Reagent-Controlled Diastereoselective Reduction of (+)- and <b>(</b><b>−</b><b>)-</b>α-Chiral Ketones with (+)- and (−)-<i>B</i>-Chlorodiisopinocampheylborane
  作者：P. Veeraraghavan Ramachandran、Guang-Ming Chen、Herbert C. Brown

  DOI：10.1021/jo951207r

  日期：1996.1.1

  Asymmetric reduction of (+)- and (-)-alpha-chiral ketones with (+)- and (-)-B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric excess, with the matched pairs providing >100:1 selectivity and the mismatched pairs showing 4:1-15:1 selectivity. The high selectivity achieved even in the mismatched pairs reveals the power of the reagent to control the stereochemical outcome. The rates of the reaction of the matched pairs are faster than those of the mismatched pairs, In all the cases studied thus far, the (-)-reagent ((d)Ipc(2)BCl) and (S)ketone or the (+)-reagent ((l)Ipc(2)BCl) and (R)-ketone constitute matched pairs and the (-)-reagent and (R)-ketone or the (+)-reagent and (S)-ketone constitute mismatched pairs, A possible mechanism for the reductions is discussed.
• Toivonen, Annales Academiae Scientiarum Fennicae, Series A2: Chemica, 1956, # 72, p. 27,32
  作者：Toivonen

  DOI：——

  日期：——

表征谱图