cupressuflavone 4',4"',7,7"-tetramethyl ether | 13738-92-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: cupressuflavone 4',4"',7,7"-tetramethyl ether
• 英文别名: 5,5''-dihydroxy-4',4''',7,7''-tetramethoxy-8,8''-biflavone；4',4''',7,7''-tetra-O-methylcupressuflavone；7,4',7'',4'''-tetra-O-methylcupressuflavone；5,5'-dihydroxy-7,7'-dimethoxy-2,2'-bis-(4-methoxy-phenyl)-[8,8']bichromenyl-4,4'-dione；4',4''',7,7''-Tetra-O-methylcupressuflavon；7,7',4',4''-Tetramethoxy-cupressuflavon；5-hydroxy-8-[5-hydroxy-7-methoxy-2-(4-methoxyphenyl)-4-oxochromen-8-yl]-7-methoxy-2-(4-methoxyphenyl)chromen-4-one
• CAS: 13738-92-6；21044-82-6；63043-61-8
• 化学式: C₃₄H₂₆O₁₀
• 分子量: 594.574
• InChiKey: KQVQZFVRSOIPIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  44
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  130
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  cupressuflavone 4',4"',7,7"-tetramethyl ether 在 氢氧化钾 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.33h， 生成 (+)-5,5''-dihydroxy-4',4''',7,7''-tetramethoxy-8,8''-biflavone
  参考文献：
  名称：

  Synthesis, Resolution, and Absolute Configuration of Optically Pure 5,5''-Dihydroxy-4',4''',7,7''-tetramethoxy-8,8''-biflavone and Its Derivatives

  摘要：

  Optically pure 5,5 ''-dihydroxy-4,4''',7,7 ''-tetramethoxy-8,8 ''-biflavone (1) and its dimethyl derivative 5 were synthesized for the first time. Resolution of the racemic (+/-)-1, prepared by a modified literature procedure, was performed via the formation and recrystallization of its (+)- and (-)-camphorsulfonate 6. Hydrolysis of the (+)- or (-)-camphorsulfonate 6 afforded optically pure (+)- or (-)-1, which was then methylated to give (+)- or (-)-5. The absolute configurations of(+)-1 and (-)-1, assigned as (aR) and (aS), respectively, were confirmed in an unambiguous manner by X-ray single crystal analysis and from their CD spectra.

  DOI：

  10.1021/jo00125a031
• 作为产物：
  描述：

  (E)-1-(2-羟基-4,6-二甲氧基苯基)-3-(4-甲氧基苯基)-2-丙烯-1-酮 在 三氯化铝 、 碘 、 碘酸 、 铜 作用下， 以 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 26.33h， 生成 cupressuflavone 4',4"',7,7"-tetramethyl ether
  参考文献：
  名称：

  Synthesis, Resolution, and Absolute Configuration of Optically Pure 5,5''-Dihydroxy-4',4''',7,7''-tetramethoxy-8,8''-biflavone and Its Derivatives

  摘要：

  Optically pure 5,5 ''-dihydroxy-4,4''',7,7 ''-tetramethoxy-8,8 ''-biflavone (1) and its dimethyl derivative 5 were synthesized for the first time. Resolution of the racemic (+/-)-1, prepared by a modified literature procedure, was performed via the formation and recrystallization of its (+)- and (-)-camphorsulfonate 6. Hydrolysis of the (+)- or (-)-camphorsulfonate 6 afforded optically pure (+)- or (-)-1, which was then methylated to give (+)- or (-)-5. The absolute configurations of(+)-1 and (-)-1, assigned as (aR) and (aS), respectively, were confirmed in an unambiguous manner by X-ray single crystal analysis and from their CD spectra.

  DOI：

  10.1021/jo00125a031

文献信息

• Total Synthesis and Absolute Stereochemistry of the Natural Atropisomer of the Biflavone 4‘,4‘‘‘,7,7‘‘-Tetra-<i>O</i>-methylcupressuflavone
  作者：Hong-Yu Li、Tatsuo Nehira、Mami Hagiwara、Nobuyuki Harada

  DOI：10.1021/jo970670w

  日期：1997.10.1

  bis(camphanate) esters. The absolute configuration of bis(camphanate) ester (-)-8b was determined to be (aR) by X-ray analysis. The ester (aR)-(-)-8b was converted to the natural biflavone [CD(+)362.0]-(-)-1, leading to the (aR) absolute configuration of 1. This conclusion is consistent with our previous theoretical determination of the absolute stereochemistry of biflavone 1 by the molecular orbital calculation

  已实现了天然阻转异构体4'，4“'，7,7”-四-O-甲基cu草黄酮（1）的全合成。通过固态苯酚偶联反应合成了关键中间体3,3'-二乙酰基-4,4'，6,6'-四甲氧基-2,2'-联苯二醇（5），外消旋体5被拆分为双（樟脑酸酯）酯。通过X射线分析确定双（樟脑酸酯）酯（-）-8b的绝对构型为（aR）。酯（aR）-（-）-8b被转化为天然双黄酮[CD（+）362.0]-（-）-1，导致（aR）的绝对构型为1。该结论与我们先前的理论相符CD光谱的分子轨道计算确定比黄酮1的绝对立体化学。
• The first enantioselective synthesis of optically pure (R)- and (S)-5,5″-dihydroxy-4′,4‴,7,7″-tetramethoxy-8,8″-biflavone and the reconfirmation of their absolute configuration
  作者：Guo-Qiang Lin、Min Zhong

  DOI：10.1016/s0040-4039(96)02475-6

  日期：1997.2

  The first enantioselective synthesis of the optically pure (R)- and (S)-5,5″-dihydroxy-4′,4‴,7,7″-tetramethoxy-8,8″-biflavone is described. The key steps involve the intramolecular oxidative coupling of the cyanocuprate intermediate and Friedel-Crafts rearrangement. Their absolute configuration was reconfirmed by CD spectra.

  描述了光学纯的（R）-和（S）-5,5“-二羟基-4'，4‴，7,7”-四甲氧基-8,8“-双黄酮的第一对映选择性合成。关键步骤涉及氰铜酸盐中间体的分子内氧化偶联和Friedel-Crafts重排。CD光谱再次证实了它们的绝对构型。
• Synthesis, Resolution, and Absolute Configuration of Optically Pure 5,5''-Dihydroxy-4',4''',7,7''-tetramethoxy-8,8''-biflavone and Its Derivatives
  作者：Fang-Jie Zhang、Guo-Qiang Lin、Qi-Chen Huang

  DOI：10.1021/jo00125a031

  日期：1995.10

  Optically pure 5,5 ''-dihydroxy-4,4''',7,7 ''-tetramethoxy-8,8 ''-biflavone (1) and its dimethyl derivative 5 were synthesized for the first time. Resolution of the racemic (+/-)-1, prepared by a modified literature procedure, was performed via the formation and recrystallization of its (+)- and (-)-camphorsulfonate 6. Hydrolysis of the (+)- or (-)-camphorsulfonate 6 afforded optically pure (+)- or (-)-1, which was then methylated to give (+)- or (-)-5. The absolute configurations of(+)-1 and (-)-1, assigned as (aR) and (aS), respectively, were confirmed in an unambiguous manner by X-ray single crystal analysis and from their CD spectra.