5'-O-(2-(2-chloro-6-nitrophenyl)ethoxycarbonyl)thymidine | 179691-39-5

• 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: 5'-O-(2-(2-chloro-6-nitrophenyl)ethoxycarbonyl)thymidine
• 英文别名: 2-(2-chloro-6-nitrophenyl)ethyl [(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl carbonate
• CAS: 179691-39-5
• 化学式: C₁₉H₂₀ClN₃O₉
• 分子量: 469.835
• InChiKey: AFOSVPBZZRICCC-ARFHVFGLSA-N

物化性质

• 密度：
  1.500±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  5'-O-(2-(2-chloro-6-nitrophenyl)ethoxycarbonyl)thymidine 以 甲醇 、 水 为溶剂， 反应 1.0h， 以80%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：

  2-氯-6-硝基甲苯 生成 5'-O-(2-(2-chloro-6-nitrophenyl)ethoxycarbonyl)thymidine
  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

• Nucleoside derivatives with photolabile protective groups
  申请人：Pfleiderer; Wolfgang

  公开号：US05763599A1

  公开（公告）日：1998-06-09

  The invention relates to nucleoside derivatives having photolabile protective groups of the general formula (I) ##STR1## in which R.sup.1 .dbd.H, NO.sub.2, CN, OCH.sub.3, halogen or alkyl or alkoxyalkyl having 1 to 4 C atoms R.sup.2 .dbd.H, OCH.sub.3 R.sup.3 .dbd.H, F, Cl, Br, NO.sub.2 R.sup.4 .dbd.H, halogen, OCH.sub.3, or an alkyl radical having 1 to 4 C atoms R.sup.5 .dbd.H or a usual functional group for preparing oligonucleotides R.sup.6 .dbd.H, OH, halogen or XR.sup.8, where X.dbd.O or S and R.sup.8 represents a protective group usual in nucleotide chemistry, B=adenine, cytosine, guanine, thymine, uracil, 2,6-diaminopurin-9-yl, hypoxanthin-9-yl, 5-methylcytosin-1-yl, 5-amino-4-imidazolcarboxamid-1-yl, or 5-amino-4-imidazolcarboxamid-3-yl, where in the case of B=adenine, cytosine or guanine, the primary amino function optionally exhibits a permanent protective group. These derivatives may be used for the light-controlled synthesis of oligonucleotides on a DNA chip.

  该发明涉及具有通式（I）的光敏保护基的核苷衍生物##STR1##其中R.sup.1 =H、NO.sub.2、CN、OCH.sub.3、卤素或具有1至4个碳原子的烷基或烷氧基烷基R.sup.2 =H、OCH.sub.3 R.sup.3 =H、F、Cl、Br、NO.sub.2 R.sup.4 =H、卤素、OCH.sub.3或具有1至4个碳原子的烷基基团R.sup.5 =H或用于制备寡核苷酸的常见功能基R.sup.6 =H、OH、卤素或XR.sup.8，其中X=O或S，R.sup.8代表核苷酸化学中常见的保护基，B=腺嘌呤、胞嘧啶、鸟嘌呤、胸腺嘧啶、尿嘧啶、2,6-二氨基嘌呤-9-基、次黄嘌呤-9-基、5-甲基胞嘧啶-1-基、5-氨基-4-咪唑甲酰胺-1-基或5-氨基-4-咪唑甲酰胺-3-基，其中在B=腺嘌呤、胞嘧啶或鸟嘌呤的情况下，初级氨基功能可选择具有永久保护基。这些衍生物可用于在DNA芯片上进行光控合成寡核苷酸。
• 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。
• 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.
• NUCLEOSID-DERIVATE MIT PHOTOLABILEN SCHUTZGRUPPEN
  申请人：Pfleiderer, Wolfgang

  公开号：EP0797580B1

  公开（公告）日：2002-04-10
• US5763599A
  申请人：——

  公开号：US5763599A

  公开（公告）日：1998-06-09