(1α,6α,8α)-8-methyl-8-chlorobicyclo<4.2.0>oct-2-en-7-one | 32348-04-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1α,6α,8α)-8-methyl-8-chlorobicyclo<4.2.0>oct-2-en-7-one
• 英文别名: 8-exo-Chloro-8-endo-methylbicyclo<4.2.0>oct-2-en-7-one；(1R,6S,8S)-8-Chloro-8-methylbicyclo[4.2.0]oct-2-en-7-one
• CAS: 32348-04-2；56084-87-8；56084-88-9；63813-94-5；63813-96-7
• 化学式: C₉H₁₁ClO
• 分子量: 170.639
• InChiKey: VLZGLBMWFFQNQR-OOZYFLPDSA-N

物化性质

• 沸点：
  260.0±28.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1α,6α,8α)-8-methyl-8-chlorobicyclo<4.2.0>oct-2-en-7-one 在 三氟甲磺酸三甲基硅酯 N-溴代丁二酰亚胺(NBS) 、 铜 、 potassium carbonate 、 氯化铵 、 锌 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 39.0h， 生成 (1S^*,2S^*,4R^*,7S^*)-Spiro<3-oxa-9-endo-methyltricyclo<5.2.0.0^2,4>nonane-8,2'-(1',3'-dioxolane)>
  参考文献：
  名称：

  Stereochemical Consequences of 6- and 8-Substitution in Reactions of Bicyclo[4.2.0]octan-7-ones

  摘要：

  Reduction (zinc/copper couple) of each epimer of 8-chloro-8-methylbicyclo[4.2.0]oct-2-en-7-one (6 and 7) gives the same product mixture containing 95% of the 8-endo-methyl compound 8. Ketalization of 8 catalyzed by TMSOTf gives the endo-methyl cyclic ethylene ketal 10 at -78-degrees-C and the exo-methyl epimer 11 (90:10) at 25-degrees-C, in contrast to beta-naphthalenesulfonic acid-catalyzed reactions. Wittig olefination of both the functionalized 8-endo-and 8-exo-methyl ketones gives only the 8-endo-methyl olefin, whereas introduction of a 6-methoxy or 6-methyl substituent favors the 8-exo configuration. A rationale for these observations is proposed.

  DOI：

  10.1021/jo00085a031
• 作为产物：
  描述：

  2-氯丙酰氯 、 1,3-环己二烯 在 三乙胺 作用下， 生成 (1α,6α,8α)-8-methyl-8-chlorobicyclo<4.2.0>oct-2-en-7-one
  参考文献：
  名称：

  Synthesis via chloroketene adducts. Synthesis of demethylsesquicarene

  摘要：

  DOI：

  10.1021/jo00445a042

文献信息

• New synthesis of (.+-.)-sirenin and a physiologically active analog
  作者：Kenn E. Harding、J. Byron Strickland、Jeffrey Pommerville

  DOI：10.1021/jo00255a045

  日期：1988.9
• Sigma assisted versus unassisted pathways in the ionization of tertiary cyclopropyl triflates
  作者：Xavier Creary

  DOI：10.1021/jo00885a018

  日期：1976.11
• Halogenated ketenes. XVI. Steric control in unsymmetrical ketone-olefin cycloadditions
  作者：William T. Brady、Robert Roe

  DOI：10.1021/ja00736a016

  日期：1971.4
• HARDING, KENN E.;STRICKLAND, J. BYRON;POMMERVILLE, JEFFREY, J. ORG. CHEM., 53,(1988) N 20, C. 4877-4883
  作者：HARDING, KENN E.、STRICKLAND, J. BYRON、POMMERVILLE, JEFFREY

  DOI：——

  日期：——
• Stereochemical Consequences of 6- and 8-Substitution in Reactions of Bicyclo[4.2.0]octan-7-ones
  作者：Helen Y. Wu、Keith A. M. Walker、Janis T. Nelson

  DOI：10.1021/jo00085a031

  日期：1994.3

  Reduction (zinc/copper couple) of each epimer of 8-chloro-8-methylbicyclo[4.2.0]oct-2-en-7-one (6 and 7) gives the same product mixture containing 95% of the 8-endo-methyl compound 8. Ketalization of 8 catalyzed by TMSOTf gives the endo-methyl cyclic ethylene ketal 10 at -78-degrees-C and the exo-methyl epimer 11 (90:10) at 25-degrees-C, in contrast to beta-naphthalenesulfonic acid-catalyzed reactions. Wittig olefination of both the functionalized 8-endo-and 8-exo-methyl ketones gives only the 8-endo-methyl olefin, whereas introduction of a 6-methoxy or 6-methyl substituent favors the 8-exo configuration. A rationale for these observations is proposed.