(E)-2-amino-6-chloro-N⁹-(3,4-bis(diethylphosphono)-2-buten-1-yl)purine | 135878-75-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: (E)-2-amino-6-chloro-N⁹-(3,4-bis(diethylphosphono)-2-buten-1-yl)purine
• 英文别名: 9-[(E)-3,4-bis(diethoxyphosphoryl)but-2-enyl]-6-chloropurin-2-amine
• CAS: 135878-75-0
• 化学式: C₁₇H₂₈ClN₅O₆P₂
• 分子量: 495.84
• InChiKey: CJESAJOCGVOHEM-UKTHLTGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.48
• 重原子数：
  31.0
• 可旋转键数：
  13.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  140.68
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为产物：
  描述：

  2-Amino-6-chloro-N⁹-(4-chloro-2-butyn-1-yl)purine 、 亚磷酸三乙酯 在 四丁基碘化铵 作用下， 反应 1.0h， 以58%的产率得到(E)-2-amino-6-chloro-N⁹-(3,4-bis(diethylphosphono)-2-buten-1-yl)purine
  参考文献：
  名称：

  Unsaturated phosphonates as acyclic nucleotide analogs. Anomalous Michaelis-Arbuzov and Michaelis-Becker reactions with multiple bond systems

  摘要：

  Reaction of adenallene (4a) with methanesulfonyl chloride in pyridine afforded 4'-chloro-4'-deoxyadenallene (6a). A similar reaction with toluene-4-sulfonyl chloride (NEt3, CH2Cl2) led to elimination of the unsaturated moiety and formation of N9-(4-toluenesulfonyl)adenine (8a). Michaelis-Arbuzov reaction of E- and Z-unsaturated chlorides 13a and 16b with triethyl phosphite afforded phosphonates 14a and 17b. Dealkylation of the latter products, coupled in case of 17b with acid hydrolysis, led to phosphonic acids 15a and 18. By contrast, Michaelis-Arbuzov reaction with butynyl chlorides 19a and 19b led to elimination of unsaturated moiety and alkylation of the released heterocyclic bases to give N9-ethyl derivatives 20a and 20b. In the presence of iodide ion, N9-(2,3-butadien-1-yl)adenine (30a, from 19a) and/or unsaturated diphosphonates 25a and 25b were obtained. The Michaelis-Arbuzov reaction of chloroallene 6a led to 2'-phosphonate 33a which, after dealkylation, afforded phosphonic acid 35a. When iodide ion was present, both 2'- and 4'-phosphonates 33a and 36a were obtained. Compound 36a was also prepared by Michaelis-Becker reaction of chloroallene 6a with sodium diethyl phosphite in THF-HMPA. In DMSO, both phosphonates 33a and 36a were formed. Under similar conditions (DMF), chlorobutyne 19a gave 4'-phosphonate 36a. Dealkylation of 36a furnished phosphonic acid 37a. Adenallene (4a) and diethyl chlorophosphite in pyridine afforded phosphonate 33a whereas butynol 39a afforded only adenine (10a). The probable reaction course of these transformations and spectral properties of the reaction products will be discussed.

  DOI：

  10.1021/jo00034a025

文献信息

• PHADTARE, SHASHIKANT;ZEMLICKA, JIRI, NUCLEOSIDES AND NUCLEOTIDES, 10,(1991) N-3, C. 275-278
  作者：PHADTARE, SHASHIKANT、ZEMLICKA, JIRI

  DOI：——

  日期：——
• Unsaturated phosphonates as acyclic nucleotide analogs. Anomalous Michaelis-Arbuzov and Michaelis-Becker reactions with multiple bond systems
  作者：Sreenivasulu Megati、Shashikant Phadtare、Jiri Zemlicka

  DOI：10.1021/jo00034a025

  日期：1992.4

  Reaction of adenallene (4a) with methanesulfonyl chloride in pyridine afforded 4'-chloro-4'-deoxyadenallene (6a). A similar reaction with toluene-4-sulfonyl chloride (NEt3, CH2Cl2) led to elimination of the unsaturated moiety and formation of N9-(4-toluenesulfonyl)adenine (8a). Michaelis-Arbuzov reaction of E- and Z-unsaturated chlorides 13a and 16b with triethyl phosphite afforded phosphonates 14a and 17b. Dealkylation of the latter products, coupled in case of 17b with acid hydrolysis, led to phosphonic acids 15a and 18. By contrast, Michaelis-Arbuzov reaction with butynyl chlorides 19a and 19b led to elimination of unsaturated moiety and alkylation of the released heterocyclic bases to give N9-ethyl derivatives 20a and 20b. In the presence of iodide ion, N9-(2,3-butadien-1-yl)adenine (30a, from 19a) and/or unsaturated diphosphonates 25a and 25b were obtained. The Michaelis-Arbuzov reaction of chloroallene 6a led to 2'-phosphonate 33a which, after dealkylation, afforded phosphonic acid 35a. When iodide ion was present, both 2'- and 4'-phosphonates 33a and 36a were obtained. Compound 36a was also prepared by Michaelis-Becker reaction of chloroallene 6a with sodium diethyl phosphite in THF-HMPA. In DMSO, both phosphonates 33a and 36a were formed. Under similar conditions (DMF), chlorobutyne 19a gave 4'-phosphonate 36a. Dealkylation of 36a furnished phosphonic acid 37a. Adenallene (4a) and diethyl chlorophosphite in pyridine afforded phosphonate 33a whereas butynol 39a afforded only adenine (10a). The probable reaction course of these transformations and spectral properties of the reaction products will be discussed.