methyl norbornane-7-carboxylate | 18468-08-1

• 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: methyl norbornane-7-carboxylate
• 英文别名: Methyl bicyclo[2.2.1]heptane-7-carboxylate
• CAS: 18468-08-1
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: RNHVBTDQHQYWDC-UHFFFAOYSA-N

物化性质

• 沸点：
  75-76 °C(Press: 10 Torr)
• 密度：
  1.079±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl norbornane-7-carboxylate 在 palladium on activated charcoal lithium aluminium tetrahydride 、 Grubbs catalyst first generation 、 正丁基锂 、 Celite 、 氢气 、 magnesium 、 1,2-二溴乙烷 、 pyridinium chlorochromate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 反应 99.0h， 生成
  参考文献：
  名称：

  通过晶体结构-固态反应相关性揭示的 1,4-羟基双自由基行为

  摘要：

  由于存在多个反应性构象异构体和构象依赖性系统间交叉的可能性，溶液中三联体 1,4-羟基双自由基的结构-反应性相关性变得困难。这些问题可以通过在结晶状态下工作来克服，其中 1,4-羟基双自由基的构象是固定的，并且可以通过母体酮的 X 射线晶体学确定，假设氢原子提取发生而构象几乎没有变化或没有变化。这种方法应用于 15 种双环和三环酮，其双自由基构象略有不同，因此可以测试几何形状的微小变化和增量变化对双自由基行为的影响。结果表明，虽然几何形状确实对 1,4-羟基双自由基在环化、裂解、

  DOI：

  10.1021/ja039076w
• 作为产物：
  描述：

  7-溴双环[2.2.1]庚烷 在 LiDBB 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 0.25h， 生成 methyl norbornane-7-carboxylate
  参考文献：
  名称：

  Synthesis of Bis(semiquinone)s and Their Electrochemical and Electron Paramagnetic Resonance Spectral Characterization

  摘要：

  The syntheses of three new bis(semiquinone)s (2(..2-), 3(..2-), and 5(..2-)) linked through carbon-carbon double bonds in a geminal fashion (2(..2-) and 3(..2-)), and through an sp(3) carbon (5(..2-)), are presented, as well as the results of variable-temperature EPR CVT-EPR) spectroscopy on these biradicals and two previously reported bis(semiquinone)s, 1(..2-) and 4(..2-). We suggest that the potential difference in redox couples associated with a biradical is useful for qualitatively assessing changes in the exchange parameter within an isostructural series. The zero-field-splitting parameters for 1(..2-)- 5(..2-) are consistent with their electronic structures: biradicals 1(..2-)-3(..2-) which have conjugating groups attached to the semiquinone rings have D-values less than 5(..2-), a bis(semiquinone) that lacks such a conjugating group. Also, the D-value of 3(..2-) is significantly less than those of 1(..2-) and 2(..2-), in greement with larger interelectron separation in 3(..2-), a biradical with quinone-methide pi-system delocalization. Changes in counterion Lewis acidity are not manifested in the D-values of the biradical dianion 4(..2-). The EPR spectrum of biradical 5(..2-) is consistent with the existence of at least two rotamers having different zero-field-splitting parameters. Biradicals 1(..2-)-4(..2-) gave linear Curie plots, consistent with J > 0 (ferromagnetic coupling) or J = 0, The temperature-dependent intensity of EPR signals of 5(..2-) are characteristic of antiferromagnetic coupling. Best fit results give J = -114 +/- 6 cal/mol for the \D/hc\ = 0.01309 cm(-1) rotamer of 5(..2-), and J = -76 +/-: 3 cal/mol for the \D/hc\ = 0.01026 cm(-1) rotamer of 5(..2-).

  DOI：

  10.1021/jo981597s

文献信息

• Preparation and some properties of 7,7-dilithionorbornane
  作者：Cornelis P. Vlaar、Gerhard W. Klumpp

  DOI：10.1016/0040-4039(91)80659-t

  日期：1991.6

  7,7-Dilithionorbornane 4a is formed from 7,7-dibromonorbornane 4b by reduction with 4,5 equiv of lithium p,p′-di-tert-butylbiphenyl at −100°C,at which temperature it adds to ethylene. On warming it rearranges to 1-1ithio-5-(2-lithioethyl)cyclopentene 5.

  7,7- Dilithionorbornane 4A是从7,7- dibromonorbornane形成图4b通过还原4,5-当量锂的P，P ' -二-叔-butylbiphenyl在-100℃，在此温度将其添加到乙烯。在加热时，它重排成1-1ithio-5-（2-lithioethyl）cyclopentene 5。
• Structure−Property Relationships in Trimethylenemethane-Type Biradicals. 2. Synthesis and EPR Spectral Characterization of Dinitroxide Biradicals
  作者：David A. Shultz、Andrew K. Boal、Hyoyoung Lee、Gary T. Farmer

  DOI：10.1021/jo990061j

  日期：1999.6.1

  Several trimethylenemethane-type (TMM-type) dinitroxide biradicals have been prepared that differ in tert-butylaminoxylphenyl ring torsion angles by virtue of different steric demands of their "spin-protecting groups". In addition, the synthesis of a TMM-type dinitroxide having a planar pi-system is reported. The synthetic route employed for the planar TMM-type biradical is general and should therefore expand, the utility of TMM-type biradicals that are susceptible to bond torsions that attenuate exchange coupling. The compounds presented are designed to be effective to map out J-coupling/conformation space in TMM-type biradicals. EPR spectroscopic parameters (hfcc and D-values) were compared to determine if their values reflected differences in conformation in the series of biradicals. Interestingly, neither N- nor H-hfcc varied within our series of biradicals/monoradicals in a regular fashion, indicating that there is no apparent relationship between N- or H-hfcc and conformation (as judged by molecular mechanics calculations). However, D-values, estimated from relative intensities of Delta m(s) = 1 and Delta m(s) = 2 transitions, are consistent with a varied degree of delocalization in the dinitroxides: smaller D-values for biradicals having smaller aryl torsions (and greater delocalization), and larger D-values for dinitroxides having greater aryl torsions (and less delocalization). All the biradicals studied, except 5(..), exhibited linear Curie plots. The linear Curie plots are consistent with both triplet ground-states and singlet-triplet degeneracies. Interestingly, dinitroxide 6(..) exhibited a linear Curie plot, despite the lack of a pi-coupling fragment. Biradical 5(..), however, is a ground-state singlet; species with the triplet lying about 140 cal/mol above the singlet.
• Synthesis of Bis(semiquinone)s and Their Electrochemical and Electron Paramagnetic Resonance Spectral Characterization
  作者：David A. Shultz、Andrew K. Boal、Gary T. Farmer

  DOI：10.1021/jo981597s

  日期：1998.12.1

  The syntheses of three new bis(semiquinone)s (2(..2-), 3(..2-), and 5(..2-)) linked through carbon-carbon double bonds in a geminal fashion (2(..2-) and 3(..2-)), and through an sp(3) carbon (5(..2-)), are presented, as well as the results of variable-temperature EPR CVT-EPR) spectroscopy on these biradicals and two previously reported bis(semiquinone)s, 1(..2-) and 4(..2-). We suggest that the potential difference in redox couples associated with a biradical is useful for qualitatively assessing changes in the exchange parameter within an isostructural series. The zero-field-splitting parameters for 1(..2-)- 5(..2-) are consistent with their electronic structures: biradicals 1(..2-)-3(..2-) which have conjugating groups attached to the semiquinone rings have D-values less than 5(..2-), a bis(semiquinone) that lacks such a conjugating group. Also, the D-value of 3(..2-) is significantly less than those of 1(..2-) and 2(..2-), in greement with larger interelectron separation in 3(..2-), a biradical with quinone-methide pi-system delocalization. Changes in counterion Lewis acidity are not manifested in the D-values of the biradical dianion 4(..2-). The EPR spectrum of biradical 5(..2-) is consistent with the existence of at least two rotamers having different zero-field-splitting parameters. Biradicals 1(..2-)-4(..2-) gave linear Curie plots, consistent with J > 0 (ferromagnetic coupling) or J = 0, The temperature-dependent intensity of EPR signals of 5(..2-) are characteristic of antiferromagnetic coupling. Best fit results give J = -114 +/- 6 cal/mol for the \D/hc\ = 0.01309 cm(-1) rotamer of 5(..2-), and J = -76 +/-: 3 cal/mol for the \D/hc\ = 0.01026 cm(-1) rotamer of 5(..2-).
• 1,4-Hydroxybiradical Behavior Revealed through Crystal Structure−Solid-State Reactivity Correlations
  作者：Dario Braga、Shuang Chen、Heather Filson、Lucia Maini、Matthew R. Netherton、Brian O. Patrick、John R. Scheffer、Carl Scott、Wujiong Xia

  DOI：10.1021/ja039076w

  日期：2004.3.1

  Structure-reactivity correlations for triplet 1,4-hydroxybiradicals in solution are made difficult by the presence of multiple reactive conformers and the possibility of conformation-dependent intersystem crossing. These problems can be overcome by working in the crystalline state, where the conformations of the 1,4-hydroxybiradicals are fixed and determinable by X-ray crystallography of the parent

  由于存在多个反应性构象异构体和构象依赖性系统间交叉的可能性，溶液中三联体 1,4-羟基双自由基的结构-反应性相关性变得困难。这些问题可以通过在结晶状态下工作来克服，其中 1,4-羟基双自由基的构象是固定的，并且可以通过母体酮的 X 射线晶体学确定，假设氢原子提取发生而构象几乎没有变化或没有变化。这种方法应用于 15 种双环和三环酮，其双自由基构象略有不同，因此可以测试几何形状的微小变化和增量变化对双自由基行为的影响。结果表明，虽然几何形状确实对 1,4-羟基双自由基在环化、裂解、