7-hydroxy-4,4,9,9-tetramethyl<12>paracyclophan-6-one | 137334-88-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-hydroxy-4,4,9,9-tetramethyl<12>paracyclophan-6-one
• 英文别名: 8-hydroxy-5,5,10,10-tetramethylbicyclo[12.2.2]octadeca-1(16),14,17-trien-7-one
• CAS: 137334-88-4
• 化学式: C₂₂H₃₄O₂
• 分子量: 330.511
• InChiKey: QGRMRBBTQYYBIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  24.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  7-hydroxy-4,4,9,9-tetramethyl<12>paracyclophan-6-one 在 甲醇 、 copper diacetate 、 sodium hexamethyldisilazane 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 36.0h， 生成 5(S*),8(S*)-dihydroxy-4,4,9,9-tetramethyl<12>paracyclophane-6,7-dione
  参考文献：
  名称：

  Synthesis and properties of 4,4,9,9-tetramethyl[12]paracyclophane-5,6,7,8-tetrone

  摘要：

  The synthesis of 4,4,9,9-tetramethyl[12]paracyclophane-5,6,7,8-tetrone (26) has been achieved in a multistep procedure. Compound 26 is the first cyclic tetraketone whose structure has been studied by X-ray analysis. The key intermediates were 4,4,9,9-tetramethyl[12]paracyclophane-6,7-dione (22), 6,7-bis[(trimethylsilyl)oxy]-4,4,9,9-tetramethyl[12]paracyclophane-5,7-diene (24), and two epimeric 5,8-dihydroxy-4,4,9,9-tetramethyl[12]-paracyclophane-6,7-diones 25a and 25b. X-ray analyses have been performed on 24, 25b and 26. That on 24 reveals a dihedral angle of 57-degrees between the two silylenol ether groups. The product analyses and the configurations of 25a and 25b together with the isolation of the bis(epoxide) intermediate 28 allow conclusions to be drawn on the oxidation mechanism of 24 with m-CPBA (Rubottom reaction). The stability of 26 is ascribed to steric factors.

  DOI：

  10.1021/jo00027a045
• 作为产物：
  描述：

  dimethyl 3,3'-(1,4-phenylene)dipropanoate 在 lithium aluminium tetrahydride 、 五氯化磷 、 氢溴酸 、 sodium 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 xylene 为溶剂， 反应 60.5h， 生成 7-hydroxy-4,4,9,9-tetramethyl<12>paracyclophan-6-one
  参考文献：
  名称：

  Synthesis and properties of 4,4,9,9-tetramethyl[12]paracyclophane-5,6,7,8-tetrone

  摘要：

  The synthesis of 4,4,9,9-tetramethyl[12]paracyclophane-5,6,7,8-tetrone (26) has been achieved in a multistep procedure. Compound 26 is the first cyclic tetraketone whose structure has been studied by X-ray analysis. The key intermediates were 4,4,9,9-tetramethyl[12]paracyclophane-6,7-dione (22), 6,7-bis[(trimethylsilyl)oxy]-4,4,9,9-tetramethyl[12]paracyclophane-5,7-diene (24), and two epimeric 5,8-dihydroxy-4,4,9,9-tetramethyl[12]-paracyclophane-6,7-diones 25a and 25b. X-ray analyses have been performed on 24, 25b and 26. That on 24 reveals a dihedral angle of 57-degrees between the two silylenol ether groups. The product analyses and the configurations of 25a and 25b together with the isolation of the bis(epoxide) intermediate 28 allow conclusions to be drawn on the oxidation mechanism of 24 with m-CPBA (Rubottom reaction). The stability of 26 is ascribed to steric factors.

  DOI：

  10.1021/jo00027a045