(7-methoxycoumarin-4-yl)methyl(diethyl)phosphate | 92543-28-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: (7-methoxycoumarin-4-yl)methyl(diethyl)phosphate
• 英文别名: diethyl (7'-methoxy-2'-oxobenzopyran-4'-yl)methyl phosphate；coumaryl diethyl phosphate；Diethyl (7-methoxy-2-oxochromen-4-yl)methyl phosphate
• CAS: 92543-28-7
• 化学式: C₁₅H₁₉O₇P
• 分子量: 342.285
• InChiKey: MASSYMBDSMTGKV-UHFFFAOYSA-N

物化性质

• 熔点：
  65 °C
• 沸点：
  471.4±45.0 °C(Predicted)
• 密度：
  1.270±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (7-methoxycoumarin-4-yl)methyl(diethyl)phosphate 在 HEPES buffer 作用下， 以 水 、 乙腈 为溶剂， 生成 磷酸二乙酯 、 4-(hydroxymethyl)-7-methoxycoumarin
  参考文献：
  名称：

  Deactivation Behavior and Excited-State Properties of (Coumarin-4-yl)methyl Derivatives. 1. Photocleavage of (7-Methoxycoumarin-4-yl)methyl-Caged Acids with Fluorescence Enhancement

  摘要：

  The photochemistry of the (7-methoxycoumarin-4-yl)methyl (MCM) carboxylates 3a-d, the mesylate 4, and the phosphates 5a-e has been examined under near physiological conditions in acetonitrile or methanol/aqueous HEPES buffer solution, respectively Analysis of photoproducts as well as measurements of photochemical quantum yields, fluorescence quantum yields, and lifetimes for the excited singlet state verified the similar photochemical and photophysical behavior of all the esters studied here. 4-(Hydroxymethyl)-7-methoxycoumarin (2) and the corresponding free acids were obtained as major products upon irradiation. The rates of deactivation of the excited MCM derivatives 3a-5e were found to be dependent on the:leaving group ability of the anion concerned as well as on the solvent polarity. The polarity dependence and the exclusive formation of O-18-labeled 2 during irradiation of 5a in O-18-labeled water indicate that photocleavage of the excited singlet state of the MCM caged compounds 3a-5e proceeds via a photo S(N)1 mechanism (solvent-assisted photoheterolysis).

  DOI：

  10.1021/jo9910233
• 作为产物：
  描述：

  4-(hydroxymethyl)-7-methoxycoumarin 、 氯磷酸二乙酯 在 吡啶 作用下， 反应 4.0h， 以78.2%的产率得到(7-methoxycoumarin-4-yl)methyl(diethyl)phosphate
  参考文献：
  名称：

  Deactivation Behavior and Excited-State Properties of (Coumarin-4-yl)methyl Derivatives. 1. Photocleavage of (7-Methoxycoumarin-4-yl)methyl-Caged Acids with Fluorescence Enhancement

  摘要：

  The photochemistry of the (7-methoxycoumarin-4-yl)methyl (MCM) carboxylates 3a-d, the mesylate 4, and the phosphates 5a-e has been examined under near physiological conditions in acetonitrile or methanol/aqueous HEPES buffer solution, respectively Analysis of photoproducts as well as measurements of photochemical quantum yields, fluorescence quantum yields, and lifetimes for the excited singlet state verified the similar photochemical and photophysical behavior of all the esters studied here. 4-(Hydroxymethyl)-7-methoxycoumarin (2) and the corresponding free acids were obtained as major products upon irradiation. The rates of deactivation of the excited MCM derivatives 3a-5e were found to be dependent on the:leaving group ability of the anion concerned as well as on the solvent polarity. The polarity dependence and the exclusive formation of O-18-labeled 2 during irradiation of 5a in O-18-labeled water indicate that photocleavage of the excited singlet state of the MCM caged compounds 3a-5e proceeds via a photo S(N)1 mechanism (solvent-assisted photoheterolysis).

  DOI：

  10.1021/jo9910233

文献信息

• Photochemistry of phosphate esters: an efficient method for the generation of electrophiles
  作者：Richard S. Givens、Bogdan Matuszewski

  DOI：10.1021/ja00334a075

  日期：1984.10

  The photochemical cleavage of benzyl diethyl phosphates has been examined in tert-butyl alcohol, which produces the corresponding benzyl tert-butyl ether as the major solvolysis product upon direct irradiation. The multiplicity of the reactive excited state has been established as the singlet state

  已经在叔丁醇中检测了磷酸苄基二乙酯的光化学裂解，在直接照射下产生相应的苄基叔丁基醚作为主要的溶剂分解产物。反应激发态的多重性已被确定为单线态
• New Photochemically Labile Protecting Group for Phosphates
  作者：Toshiaki Furuta、Hiromi Torigai、Tomoko Osawa、Michiko Iwamura

  DOI：10.1246/cl.1993.1179

  日期：1993.7

  New photochemically labile phosphate protecting group was developed. These phosphate esters have high molar extinction coefficient (e340 = 34500 dm3 mol−1 cm−1) and rapidly release parent phosphates upon irradiation ( >300 nm) with high quantum efficiency for disappearance (φdis = 0.22 at 340 nm).

  开发了新的光化学不稳定的磷酸盐保护基团。这些磷酸酯具有高摩尔消光系数 (e340 = 34500 dm3 mol−1 cm−1) 并在辐照后快速释放母体磷酸盐 (>300 nm)，具有高量子效率消失 (φdis = 0.22 at 340 nm)。
• Furuta, Toshiaki; Torigai, Hiromi; Osawa, Tomoko, Journal of the Chemical Society. Perkin transactions I, 1993, # 24, p. 3139 - 3142
  作者：Furuta, Toshiaki、Torigai, Hiromi、Osawa, Tomoko、Iwamura, Michiko

  DOI：——

  日期：——
• Deactivation Behavior and Excited-State Properties of (Coumarin-4-yl)methyl Derivatives. 1. Photocleavage of (7-Methoxycoumarin-4-yl)methyl-Caged Acids with Fluorescence Enhancement
  作者：Björn Schade、Volker Hagen、Reinhard Schmidt、Ralph Herbrich、Eberhard Krause、Torsten Eckardt、Jürgen Bendig

  DOI：10.1021/jo9910233

  日期：1999.12.1

  The photochemistry of the (7-methoxycoumarin-4-yl)methyl (MCM) carboxylates 3a-d, the mesylate 4, and the phosphates 5a-e has been examined under near physiological conditions in acetonitrile or methanol/aqueous HEPES buffer solution, respectively Analysis of photoproducts as well as measurements of photochemical quantum yields, fluorescence quantum yields, and lifetimes for the excited singlet state verified the similar photochemical and photophysical behavior of all the esters studied here. 4-(Hydroxymethyl)-7-methoxycoumarin (2) and the corresponding free acids were obtained as major products upon irradiation. The rates of deactivation of the excited MCM derivatives 3a-5e were found to be dependent on the:leaving group ability of the anion concerned as well as on the solvent polarity. The polarity dependence and the exclusive formation of O-18-labeled 2 during irradiation of 5a in O-18-labeled water indicate that photocleavage of the excited singlet state of the MCM caged compounds 3a-5e proceeds via a photo S(N)1 mechanism (solvent-assisted photoheterolysis).