(5R,9R)-4,4,9-tribromo-1,6-dioxaspiro[4.4]nonane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5R,9R)-4,4,9-tribromo-1,6-dioxaspiro[4.4]nonane
• 化学式: C₇H₉Br₃O₂
• 分子量: 364.859
• InChiKey: MFCNKGHMUQYAAN-IYSWYEEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 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：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,6-二氧杂螺[4.4]壬烷 在 溴 、 calcium carbonate 作用下， 以 四氯化碳 为溶剂， 生成 (5R,9R)-4,4,9-tribromo-1,6-dioxaspiro[4.4]nonane 、 (5R,9S)-4,4,9-tribromo-1,6-dioxaspiro[4.4]nonane
  参考文献：
  名称：

  .alpha.-Bromo spiroketals: stereochemistry and elimination reactions

  摘要：

  The simple spiroketals, 1,6-dioxaspiro[4.4]nonane (2), 1,6-dioxaspiro[4.5]decane (5), 1,7-dioxaspiro[5.5]undecane (6), and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (7), have been brominated by bromine in carbon tetrachloride/calcium carbonate or acetic acid, and a number of mono-, di-, and tribromo derivatives have been characterized. The relative stereochemistries have been established by correlated H-1 and C-13 NMR spectroscopy and X-ray crystal structure determinations. Dehydrobromination with potassium tert-butoxide in either dimethyl sulfoxide or tetrahydrofuran is facile for the axial monobromides, although both axial and equatorial bromides derived from 1,6-dioxaspiro[4.5]decane (5) and 1,7-dioxaspiro[5.5]undecane (6) dehydrobrominate to provide 1,6-dioxaspiro[4.5]dec-9-ene (35) and 1,7-dioxaspiro[5.5]undec-4-ene (26), respectively. Hydration of these readily acquired alkenes furnishes the corresponding 9- and 4-ols, respectively, with the latter being components of the rectal glandular secretion of Bactrocera oleae (olive fly), Bactrocera cacuminatus, and Bactrocera distincta. These studies indicate that alpha-bromination of suitable spiroketals may be a viable later step in the synthesis of alpha-bromine-containing spiroketal metabolites such as obtusin and neoobtusin.

  DOI：

  10.1021/jo00061a025

文献信息

• .alpha.-Bromo spiroketals: stereochemistry and elimination reactions
  作者：Elvie N. Lawson、William Kitching、Colin H. L. Kennard、Karl A. Byriel

  DOI：10.1021/jo00061a025

  日期：1993.4

  The simple spiroketals, 1,6-dioxaspiro[4.4]nonane (2), 1,6-dioxaspiro[4.5]decane (5), 1,7-dioxaspiro[5.5]undecane (6), and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (7), have been brominated by bromine in carbon tetrachloride/calcium carbonate or acetic acid, and a number of mono-, di-, and tribromo derivatives have been characterized. The relative stereochemistries have been established by correlated H-1 and C-13 NMR spectroscopy and X-ray crystal structure determinations. Dehydrobromination with potassium tert-butoxide in either dimethyl sulfoxide or tetrahydrofuran is facile for the axial monobromides, although both axial and equatorial bromides derived from 1,6-dioxaspiro[4.5]decane (5) and 1,7-dioxaspiro[5.5]undecane (6) dehydrobrominate to provide 1,6-dioxaspiro[4.5]dec-9-ene (35) and 1,7-dioxaspiro[5.5]undec-4-ene (26), respectively. Hydration of these readily acquired alkenes furnishes the corresponding 9- and 4-ols, respectively, with the latter being components of the rectal glandular secretion of Bactrocera oleae (olive fly), Bactrocera cacuminatus, and Bactrocera distincta. These studies indicate that alpha-bromination of suitable spiroketals may be a viable later step in the synthesis of alpha-bromine-containing spiroketal metabolites such as obtusin and neoobtusin.