cis-phenyl ester of thymidine 3',5'-cyclic monophosphate | 108146-36-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-phenyl ester of thymidine 3',5'-cyclic monophosphate
• 英文别名: cis-thymidine 3',5'-cyclic phenyl monophosphate
• CAS: 108146-36-7
• 化学式: C₁₆H₁₇N₂O₇P
• 分子量: 380.294
• InChiKey: ROIXHPCABIZYBP-NOCQENOTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.15
• 重原子数：
  26.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  109.11
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  cis-phenyl ester of thymidine 3',5'-cyclic monophosphate 以 水 为溶剂， 生成 胸腺嘧啶
  参考文献：
  名称：

  Oivanen, Mikko; Varila, Jaana; Hankamaki, Teemu, Collection of Czechoslovak Chemical Communications, 1996, vol. 61, p. S26 - S29

  摘要：

  DOI：
• 作为产物：
  描述：

  cis-thymidine 3',5'-cyclic phenyl phosphite 在 二氧化氮 作用下， 以 二氯甲烷 为溶剂， 以88%的产率得到cis-phenyl ester of thymidine 3',5'-cyclic monophosphate
  参考文献：
  名称：

  The question of chair-twist equilibria for the phosphate rings of nucleoside cyclic 3',5'-monophosphates. Proton NMR and x-ray crystallographic study of the diastereomers of thymidine phenyl cyclic 3',5'-monophosphate

  摘要：

  DOI：

  10.1021/ja00247a036

文献信息

• Hydrolysis of the <i>cis</i>-Phenyl Ester of Thymidine 3‘,5‘-Cyclic Monophosphate:  pH-Dependent Competition between Depyrimidination and Phosphotriester Hydrolysis <i>via</i> CO and PO Bond Ruptures
  作者：Jaana Varila、Teemu Hankamäki、Mikko Oivanen、Leo H. Koole、Harri Lönnberg

  DOI：10.1021/jo960693v

  日期：1997.2.1

  Hydrolytic reactions of the cis-phenyl ester of thymidine 3',5'-cyclic monophosphate (In) have been followed by HPLC over a wide pH range. Under acidic conditions (pH < 4) two reactions compete: depyrimidination (cleavage of the N-glycosidic bond) and phosphotriester hydrolysis to a mixture of three phosphodiesters, viz. thymidine 3',5'-cyclic monophosphate (2) and thymidine 3'- and 5'-(phenyl phosphates) (3 and 4). Depyrimidination predominates (>80%) at pH < 1 and shows first-order dependence on acidity. The reaction is 4.5 to 5 times slower than with 2. The phosphotriester hydrolysis of 1a is acid catalyzed at pH < 2, giving all three phosphodiester products (2-4). Over a broad acidity range from pH 2 to 7, the reaction is pH-independent. In this pH region, the predominant product is 3 (up to 85%). At pH > 10, the hydrolysis is hydroxide-ion-catalyzed, yielding the three phosphodiester products in a 42:42:16 ratio ([2]:[3]:[4]). From pH 7 to 10, the pH-rate profile is nonlinear, possibly due to N3H deprotonation of the thymine moiety. In the same pH range, the site of bond cleavage appears to be changed. The product analyses of the corresponding methanolysis reactions suggest that the pH-independent reaction predominantly takes place via cleavage of the C5'O bond, while the alkaline reaction proceeds by rupture of one of the PO bonds. Consistent with this proposal, the pH-independent hydrolysis yields at high concentrations of sodium chloride 5'-chloro-5'-deoxythymidine 3'-(phenyl phosphate) and in concentrated acetate buffers 5'-O-acetylthymidin 3'-(phenyl phosphate). Accordingly, the hydrolytic reactions of 1a markedly differ from those of more simple 2-aryloxy-2-oxo-1,3,2-dioxaphosphorinanes.