3-methoxy-1,6-methano<10>annulene | 83845-00-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methoxy-1,6-methano<10>annulene
• 英文别名: 3-Methoxy-1,6-methano[10]annulene；3-methoxybicyclo[4.4.1]undeca-1(10),2,4,6,8-pentaene
• CAS: 83845-00-5
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: JDSAMGUQTGDMFX-UHFFFAOYSA-N

物化性质

• 沸点：
  384.2±11.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  3-methoxy-1,6-methano<10>annulene 在 正丁基锂 、 copper dichloride 作用下， 生成 3,3'-dimethoxy-2,2'-bi(1,6-methano<10>annulenyl)
  参考文献：
  名称：

  Stereochemistry of planarchiral compounds, XIV. Static and dynamic stereochemistry of 3,3?-dimethoxy-2,2?-bi(1,6-methano[10]annulenyl)

  摘要：

  The title compound 6 was prepared from 3-methoxy-1,6-methano[10]annulene (4) via lithiation and oxidative coupling of the intermediate 5 with copper(II)chloride. Three stereoisomers (two rotamers of the racemate, 6a and 6b, and the meso-form 6c) were obtained and their configurations assigned both by H-1 NMR spectroscopy and by X-ray crystal structure analysis of 6a.Starting the reaction sequence from optically active 2-bromo-1,6-methano[10]annulene, (-)-3, of known absolute chirality (S)p established the absolute stereochemistry of (+)-6a as (R)p(R)a(R)p and (R)p(S)a(R)p for the dextrorotatory rotamer 6b. 3-Methoxy-1,6-methanol[10]annulene (4) as well as 6a and 6b were easily resolved by enantioselective chromatography of the racemic mixtures on cellulose triacetate (CTA) in ethanol. A rotational barrier of DELTAG# = 132 kJ . mol-1 between 6a and 6b was determined both by thermal equilibration and by CD-kinetics.Finally, also the meso-form 6c - because of its high rotational barrier (118 kJ) - could be resolved on CTA in its enantiomers ([alpha]D = 200-degrees in ethanol). From chiroptical comparison (CD) with 6a and 6b, resp., the chirality (R)p(S)a(S)p was deduced for (+)-6c.

  DOI：

  10.1007/bf01277640
• 作为产物：
  描述：

  1-(2,2-dibromovinyl)-6-vinylcyclohepta-1,3,5-triene 以 六甲基磷酰三胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 3-methoxy-1,6-methano<10>annulene
  参考文献：
  名称：

  Applications of MCD spectroscopy: MO ordering and transannular interaction in 1,6-methano[10]annulenes from analysis of substituent effects

  摘要：

  DOI：

  10.1021/ja00349a001

文献信息

• Meyer A., Schloegl K., Essert T., Joerrens F., Klug W., Lex J., Schmickle+, Monatsh. Chem, 125 (1994) N 6-7, S 783-790
  作者：Meyer A., Schloegl K., Essert T., Joerrens F., Klug W., Lex J., Schmickle+

  DOI：——

  日期：——
• Applications of MCD spectroscopy: MO ordering and transannular interaction in 1,6-methano[10]annulenes from analysis of substituent effects
  作者：Kenneth A. Klingensmith、Wilhelm Puettmann、Emanuel Vogel、Josef Michl

  DOI：10.1021/ja00349a001

  日期：1983.6
• Stereochemistry of planarchiral compounds, XIV. Static and dynamic stereochemistry of 3,3?-dimethoxy-2,2?-bi(1,6-methano[10]annulenyl)
  作者：A. Meyer、K. Schl�gl、T. Essert、F. J�rrens、W. Klug、J. Lex、H. Schmickler、E. Vogel

  DOI：10.1007/bf01277640

  日期：1994.6

  The title compound 6 was prepared from 3-methoxy-1,6-methano[10]annulene (4) via lithiation and oxidative coupling of the intermediate 5 with copper(II)chloride. Three stereoisomers (two rotamers of the racemate, 6a and 6b, and the meso-form 6c) were obtained and their configurations assigned both by H-1 NMR spectroscopy and by X-ray crystal structure analysis of 6a.Starting the reaction sequence from optically active 2-bromo-1,6-methano[10]annulene, (-)-3, of known absolute chirality (S)p established the absolute stereochemistry of (+)-6a as (R)p(R)a(R)p and (R)p(S)a(R)p for the dextrorotatory rotamer 6b. 3-Methoxy-1,6-methanol[10]annulene (4) as well as 6a and 6b were easily resolved by enantioselective chromatography of the racemic mixtures on cellulose triacetate (CTA) in ethanol. A rotational barrier of DELTAG# = 132 kJ . mol-1 between 6a and 6b was determined both by thermal equilibration and by CD-kinetics.Finally, also the meso-form 6c - because of its high rotational barrier (118 kJ) - could be resolved on CTA in its enantiomers ([alpha]D = 200-degrees in ethanol). From chiroptical comparison (CD) with 6a and 6b, resp., the chirality (R)p(S)a(S)p was deduced for (+)-6c.