phosphodiester of 4,4'-methylenebis(3-hydroxy-2-naphthoic acid) | 173378-34-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: phosphodiester of 4,4'-methylenebis(3-hydroxy-2-naphthoic acid)
• 英文别名: 14-Hydroxy-14-oxo-13,15-dioxa-14lambda5-phosphapentacyclo[14.8.0.03,12.04,9.019,24]tetracosa-1(16),3(12),4,6,8,10,17,19,21,23-decaene-11,17-dicarboxylic acid；14-hydroxy-14-oxo-13,15-dioxa-14λ5-phosphapentacyclo[14.8.0.03,12.04,9.019,24]tetracosa-1(16),3(12),4,6,8,10,17,19,21,23-decaene-11,17-dicarboxylic acid
• CAS: 173378-34-2
• 化学式: C₂₃H₁₅O₈P
• 分子量: 450.341
• InChiKey: BHMIKDFABXEPGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  32
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  130
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  phosphodiester of 4,4'-methylenebis(3-hydroxy-2-naphthoic acid) 在 水 作用下， 生成 3-Hydroxy-4-(2-hydroxy-2,4-dioxo-4H-1,3-dioxa-2λ⁵-phospha-anthracen-9-ylmethyl)-naphthalene-2-carboxylic acid
  参考文献：
  名称：

  Hydrolysis of a Phosphate Diester by Simultaneous Carboxylate and Carboxyl Group Participation in a Rigid System with Kinetically Unfavorable Rotamers Frozen Out

  摘要：

  DOI：

  10.1021/ja00117a044
• 作为产物：
  描述：

  帕莫酸 在 五氯化磷 、 三氯氧磷 作用下， 反应 4.0h， 生成 phosphodiester of 4,4'-methylenebis(3-hydroxy-2-naphthoic acid)
  参考文献：
  名称：

  Participation of Two Carboxyl Groups in Phosphodiester Hydrolysis. 2. A Kinetic, Isotopic, and 31P NMR Study of the Hydrolysis of a Phosphodiester with Carboxyl Groups Fixed in an Attack Conformation

  摘要：

  The phosphodiesters of 4,4'-methylenebis(3-hydroxy-2-naphthoic acid) (4) and 3-carboxy-2,2'-dihydroxy-diphenylmethane (5) are constrained into a cyclic structure such that the oxygens of the two o-carboxy groups of 4 and the single o-carboxy group of 5 have restricted stereospecific positions with an o-CO2- oxygen to phosphorus distance of 3.7 Angstrom. In the hydrolysis of 4, P-31 NMR and HPLC data show the existence of an intermediate cyclic acyl phosphate in the g,g conformation. The O-18 isotopic effects on P-31 chemical shifts show incorporation of two O-18 atoms in the product H3PO4. This observation is consistent with intramolecular o-CO2- nucleophilic attack on phosphorus to provide an acyl phosphate intermediate which undergoes hydrolytic cleavage by HO-/(HO-)-O-18 attack on phosphorus (one O-18 incorporation) to provide a phosphate monoester which also undergoes hydrolysis with a second O-18 incorporation on phosphorus. For hydrolysis of 4, the pH vs log k(obsd) profile, the values of the deuterium solvent kinetic isotope effect, and the activation entropy accord a mechanism which involves intramolecular attack of o-CO2- on the phosphate phosphorus assisted by the o-CO2H as a general acid catalyst, The latter can involve o-CO2H hydrogen bonding to the -(PO2-)- oxygen(s) and/or leaving phenolic oxygen. At neutrality, 4 hydrolyzes ca. 10(4) fold faster than 5 which only has one o-carboxy group and 10(8)-10(9)-fold faster than diphenyl phosphate.

  DOI：

  10.1021/ja00154a006

文献信息

• Participation of Two Carboxyl Groups in Phosphodiester Hydrolysis. 2. A Kinetic, Isotopic, and 31P NMR Study of the Hydrolysis of a Phosphodiester with Carboxyl Groups Fixed in an Attack Conformation
  作者：Thomas C. Bruice、Andrei Blasko、Ramesh D. Arasasingham、Jang-Seob Kim

  DOI：10.1021/ja00154a006

  日期：1995.12

  The phosphodiesters of 4,4'-methylenebis(3-hydroxy-2-naphthoic acid) (4) and 3-carboxy-2,2'-dihydroxy-diphenylmethane (5) are constrained into a cyclic structure such that the oxygens of the two o-carboxy groups of 4 and the single o-carboxy group of 5 have restricted stereospecific positions with an o-CO2- oxygen to phosphorus distance of 3.7 Angstrom. In the hydrolysis of 4, P-31 NMR and HPLC data show the existence of an intermediate cyclic acyl phosphate in the g,g conformation. The O-18 isotopic effects on P-31 chemical shifts show incorporation of two O-18 atoms in the product H3PO4. This observation is consistent with intramolecular o-CO2- nucleophilic attack on phosphorus to provide an acyl phosphate intermediate which undergoes hydrolytic cleavage by HO-/(HO-)-O-18 attack on phosphorus (one O-18 incorporation) to provide a phosphate monoester which also undergoes hydrolysis with a second O-18 incorporation on phosphorus. For hydrolysis of 4, the pH vs log k(obsd) profile, the values of the deuterium solvent kinetic isotope effect, and the activation entropy accord a mechanism which involves intramolecular attack of o-CO2- on the phosphate phosphorus assisted by the o-CO2H as a general acid catalyst, The latter can involve o-CO2H hydrogen bonding to the -(PO2-)- oxygen(s) and/or leaving phenolic oxygen. At neutrality, 4 hydrolyzes ca. 10(4) fold faster than 5 which only has one o-carboxy group and 10(8)-10(9)-fold faster than diphenyl phosphate.
• Hydrolysis of a Phosphate Diester by Simultaneous Carboxylate and Carboxyl Group Participation in a Rigid System with Kinetically Unfavorable Rotamers Frozen Out
  作者：Thomas C. Bruice、Andrei Blasko、Ramesh D. Arasasingham、Jang-Seob Kim、Mark E. Petyak

  DOI：10.1021/ja00117a044

  日期：1995.3