thymidine 5'-[2-(2-nitrophenyl)propyl carbonate] | 189216-59-9

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: thymidine 5'-[2-(2-nitrophenyl)propyl carbonate]
• 英文别名: 5'-O-[2-(o-nitrophenyl)prop-1-yloxycarbonyl]thymidine；NPPOC-Thy；5'-O-(2-(2-nitrophenyl)propoxycarbonyl)thymidine；[(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl 2-(2-nitrophenyl)propyl carbonate
• CAS: 189216-59-9
• 化学式: C₂₀H₂₃N₃O₉
• 分子量: 449.417
• InChiKey: QHGKQWGEQLZJSD-GUPZPADCSA-N

物化性质

• 密度：
  1.411±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  160
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  thymidine 5'-[2-(2-nitrophenyl)propyl carbonate] 以 甲醇 、 水 为溶剂， 反应 0.17h， 以76%的产率得到beta-胸苷
  参考文献：
  名称：

  New Photolabile Protecting Groups of the 2-(2-Nitrophenyl)ethoxycarbonyl- and the 2-(2-Nitrophenyl)ethylsulfonyl-Type for the Oligonucleotide Synthesis

  摘要：

  DOI：

  10.1080/07328319908044692
• 作为产物：
  描述：

  硝基乙苯 生成 thymidine 5'-[2-(2-nitrophenyl)propyl carbonate]
  参考文献：
  名称：

  New Photolabile Protecting Groups in Nucleoside and Nucleotide Chemistry—Synthesis, Cleavage Mechanisms and Applications

  摘要：

  New photolabile protecting groups have been found in the 2-(2-nitrophenyl)ethoxycarbonyl and the 2-(2-nitrophenyl)ethylsulfonyl group, respectively. The influence of substituents at the phenyl ring as well as the side-chain has been investigated regarding the photolysis rates on irradiation at 365 mn. beta-Branching in the side-chain leads to highly increased rates of photodeprotection. A new type of photocleavage mechanism consisting of a photoinduced beta-elimination process is proposed.

  DOI：

  10.1080/07328319808004738

文献信息

• 一种碳酸酯类光敏试剂及其制备方法、5`-光敏保护核苷的制备方法
  申请人：石平

  公开号：CN105968016A

  公开（公告）日：2016-09-28

  本发明涉及一种碳酸酯类光敏试剂及其制备方法、5'‑光敏保护核苷的制备方法。碳酸酯类光敏试剂，其结构式为：其中X为-OX’、咪唑基、取代咪唑基；5'-光敏保护核苷的制备方法步骤包括将2’-脱氧核苷与2-邻硝基苯-1-丙基碳酸酯类光敏试剂和三乙胺得5'-光敏保护核苷粗产物、粗产物提纯得到5'-光敏保护核苷。本发明5'-光敏保护核苷制备方法选择性平均提高了3.4倍，减化了提纯过程，提高了产率，大大降低了生产成本，同时避免了使用剧毒的双光气。
• New Types of Very Efficient Photolabile Protecting Groups Based upon the[2-(2-Nitrophenyl)propoxy]carbonyl (NPPOC) Moiety
  作者：Sigrid Bühler、Irene Lagoja、Heiner Giegrich、Klaus-Peter Stengele、Wolfgang Pfleiderer

  DOI：10.1002/hlca.200490060

  日期：2004.3

  in a broad range depending on the substituents. So far, the thymidine 5′-[2-(5-halo-2-nitrophenyl)propyl carbonates] 127–129, 5′-[2-(nitro[1,1′-biphenyl]3-yl)propyl carbonates] 136–139, 5′-2-[2-nitro-5-(thianthren-1-yl)phenyl]propyl carbonate} (140), 5′-[2-(5-naphthalenyl-2-nitrophenyl)propyl carbonates] 141 and 142, and 5′-[2-(2-nitro-5-thienylphenyl)propyl carbonates] 143 and 144 showed the best

  基于光不稳定的[2-（2-硝基苯基）丙氧基]羰基（NPPOC），大量修饰的2-（2-硝基苯基）丙醇衍生物在苯环上被取代（参见23 – 34和57 – 76），以及在侧链上（见85 – 92和95 – 98）被合成以改善这种新型的光不稳定实体的光反应性。苯基部分也被萘基（请参阅102、103、105、108、110、113和114），噻吩基取代基（请参阅115、117、118和120）和苯并噻吩基取代基（请参见115、117、118和113）进行交换。121）。的2-（2- nitroaryl-和杂芳基）丙醇转化用双光气成相应carbonochloridates，其与胸苷随后反应胸苷5' - （被保护的碳酸酯）123 - 178作为主要的反应产物。在某些情况下，相应的3'-碳酸酯和3'，5'-二碳酸酯179 – 212也被分离出来并进行了表征。在标准条件下的光解研究（见表）表明，光裂解的速率
• Photolabile Protecting Groups for Nucleosides: Mechanistic Studies of the 2-(2-Nitrophenyl)ethyl Group
  作者：Stefan Walbert、Wolfgang Pfleiderer、Ulrich E. Steiner

  DOI：10.1002/1522-2675(20010613)84:6<1601::aid-hlca1601>3.0.co;2-s

  日期：2001.6.13

  characterized in the 0.1 ‐ 10 ms time region. In general, two reaction channels compete for the aci-nitro compound and its anion: b-elimination of the caged compound occurs from the anion, while from the undissociated aci-nitro compound, a nitrosobenzene derivative is formed with no release of the caged compound. The yield ratio of these two reaction channels can be controlled through shifts in the protolytic

  通过纳秒激光闪光光解和固定照明实验以及量子产率和产物分布的定量 HPLC 分析，研究了几种 2-(2-硝基苯基) 乙基笼化合物（包括笼状胸苷核苷）的光化学。通过分别改变 MeCN/H2O 混合物中的 H2O 含量和 HCl 浓度来研究溶剂碱度和酸度的影响。对于所研究的所有化合物 1-7，发现通过硝基从环外 a 位相对于芳基部分夺取分子内 H 是主要过程。生成的硝基化合物的质子解离平衡在 0.1 - 10 ms 时间范围内进行动力学表征。通常，两个反应通道竞争硝基化合物及其阴离子：笼形化合物的 b-消除从阴离子发生，而从未解离的酸硝基化合物中，形成亚硝基苯衍生物，不释放笼形化合物。这两个反应通道的产率可以通过改变酸硝基化合物的质子解离平衡来控制。在具有低碱度（无 H2O 的 MeCN）或高酸度（H2O/MeCN 中的 HCl 浓度较高）的溶液中，会形成两种尚未确定的产品，每种产品都专门针对上述条件之一。
• Method for photolytically deprotecting immobilized nucleoside derivatives, especially in the production of DNA chips
  申请人：NIGU CHEMIE GMBH

  公开号：US20020053508A1

  公开（公告）日：2002-05-09

  The invention relates to a method for the specific photolytic deprotection of nucleoside derivatives that are immobilized on a substrate, especially for use in the production of DNA chips. Said method is characterized in that a gel or viscous liquid layer is applied on the nucleoside derivatives that are immobilized on a substrate. Said gel or viscous liquid contains one or more polymer compounds and at least one representative from the group comprising water, water/C 1 -C 4 alcohol mixtures and polar aprotic solvents. For initiating the deprotection, the nucleoside derivates are irradiated. This method favors a rapid, clean and complete removal of the photolabile protective groups from the nucleoside derivatives, which results in the required purity of the synthesized nucleotide or oligonucleotide sequences.

  本发明涉及一种对固定在基底上的核苷衍生物进行特定光解保护的方法，特别是用于生产 DNA 芯片。该方法的特点是在固定在基底上的核苷衍生物上涂敷一层凝胶或粘稠液体。所述凝胶或粘稠液体含有一种或多种高分子化合物，以及至少一种由水、水/C 1 -C 4 醇混合物和极性钝化溶剂。为了启动脱保护，核苷衍生物需要经过辐照。这种方法有利于快速、干净、彻底地去除核苷衍生物上的光敏保护基团，从而使合成的核苷酸或寡核苷酸序列达到所需的纯度。
• Photolabile protecting groups for nucleosides: Synthesis and photodeprotection rates
  作者：Ahmad Hasan、Klaus-Peter Stengele、Heiner Giegrich、Paul Cornwell、Kenneth R. Isham、Richard A. Sachleben、Wolfgang Pfleiderer、Robert S. Foote

  DOI：10.1016/s0040-4020(97)00154-3

  日期：1997.3

  o-Nitrobenzyloxycarbonyl and a number of related groups have been tested for the photolabile protection of nucleoside 5'-hydroxyls. The rates of photodeprotection were found to vary by approximately 17 fold in a series of 5'-O-protected thymidine derivatives irradiated at 365 nm under identical conditions. The homologous 2-(o-nitrophenyl)ethoxycarbonyl group and its derivatives were found to be removed approximately 2-fold faster than the corresponding o-nitrobenzyloxycarbonyl group, possibly due to an increased rare of alpha-hydrogen abstraction by the photo-excited nitro group. Photolysis rates were affected by substitutions on both the phenyl ring and alpha-carbon, with the strongest rate enhancements caused by the presence of a methyl or second o-nitrophenyl group in the alpha-position. Among the ring-substituted derivatives studied, o-nitro and o-iodo had the strongest enhancement effects on photodeprotection, while an o-fluoro group reduced the rate of photodeprotection. In general, substitutions at other positions on the phenyl ring had less effect on photolysis rates. (C) 1997 Elsevier Science Ltd.