[(α-methyl-2-nitropiperonyl)oxy]carbonylthymidine | 156876-22-1

• 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: [(α-methyl-2-nitropiperonyl)oxy]carbonylthymidine
• 英文别名: [(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl 1-(6-nitro-1,3-benzodioxol-5-yl)ethyl carbonate
• CAS: 156876-22-1
• 化学式: C₂₀H₂₁N₃O₁₁
• 分子量: 479.4
• InChiKey: NIILVXNDTQOBHV-VQKLMROVSA-N

物化性质

• 密度：
  1.531±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  179
• 氢给体数：
  2
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  [(α-methyl-2-nitropiperonyl)oxy]carbonylthymidine 以 甲醇 、 水 为溶剂， 生成 beta-胸苷
  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
• 作为产物：
  描述：

  3,4-亚甲二氧苯乙酮 在 吡啶 、 sodium tetrahydroborate 、 硝酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 溶剂黄146 、 甲苯 为溶剂， 反应 49.25h， 生成 [(α-methyl-2-nitropiperonyl)oxy]carbonylthymidine
  参考文献：
  名称：

  玻璃基板上 DNA 阵列的光定向合成效率

  摘要：

  基于光刻和表面荧光的新方法用于确定使用光不稳定 5'-(((α-methyl-2-nitropiperonyl)oxy)carbonyl)(MeNPOC)-2'-的光导向寡核苷酸合成的光脱保护速率和逐步产率平面玻璃基板上的脱氧核苷亚磷酰胺。在来自汞光源的近紫外线照射（主要是 365 nm）下，发现 MeNPOC 保护基团的光去除率与生长的寡聚体的核苷酸和长度无关（t1/2 = 12 s，27.5 mW /cm2）。观察到对溶剂极性的适度依赖性，在存在非极性溶剂或不存在溶剂的情况下，光解进行得最快（例如，t1/2 = 10-13 s，27.5 mW/cm2）。在解决方案中，光解速率在 5-50 mW/cm2 范围内与光强度呈线性关系。使用基于 N6-(苯氧基乙酰基)-2'-脱氧腺苷的单体合成十二聚体寡核苷酸的平均逐步产率在 92-94% 的范围内。

  DOI：

  10.1021/ja964427a

文献信息

• Protection and Labelling of Thymidine by a Fluorescent Photolabile Group
  作者：Caroline Muller、Pascale Even、Marie-Laure Viriot,、Marie-Christiane Carré

  DOI：10.1002/1522-2675(20011219)84:12<3735::aid-hlca3735>3.0.co;2-a

  日期：2001.12.19

  A fluorescent photolabile group including coumarin and MeNPOC moieties was synthesized to protect 5'-OH terminal function of thymidine (T). Its photochemical and photophysical properties were studied, in particular the photocleavage (photodeprotection under a 365-nm irradiation) is only lowered by a factor of two by addition of the fluorophore, Fluorescence properties of the coumarin probe are not changed upon irradiation, which is satisfactory for the application required, i.e., in situ synthesis of DNA microarrays.
• Comparison of Methods for Photochemical Phosphoramidite-Based DNA Synthesis
  作者：Michael C. Pirrung、Jean-Claude Bradley

  DOI：10.1021/jo00125a010

  日期：1995.10

  Toward the goal of preparing surface-bound arrays of short oligonucleotides using light-directed synthesis, we have studied novel photoremovable protecting groups for solid-phase DNA synthesis. We have protected the 5'-hydroxyls of all four nucleosides with our recently-described 3',5'-dimethoxybenzoin carbonate (DMB-carbonate) group and converted the products to (cyanoethyl)phosphoramidites. For comparison with another recently-described method for photochemical DNA synthesis, we have prepared the methylnitropiperonyl carbonate (MeNPOC) derivative of thymidine and its amidite. To permit chain attachment to supports, the thymidine DMB-carbonate succinoyl derivative was also prepared. High cycle yields (based on release of the photoproduct dimethoxyphenylbenzofuran) were obtained in initial photochemical DNA synthesis studies with DMB-carbonates. An increase in the deprotection half-life was seen with increasing oligomer length, but this effect was scale-dependent and should be minimal at the small scale at which most DNA arrays will be prepared. The oligonucleotides resulting from these syntheses contained some impurities. It was shown that 350 nm irradiation does not produce thymine dimers but does damage benzoylcytidine. This problem is solved through a change of protecting groups. However, other factors also affect the quality of the DNA prepared by photochemical synthesis, since direct comparisons between short oligomers of thymine prepared with DMTr, DMB-carbonate, and MeNPOC protecting groups show that photochemical deprotection results in diminished cycle yields compared to acid deprotection.
• The Efficiency of Light-Directed Synthesis of DNA Arrays on Glass Substrates
  作者：Glenn H. McGall、Anthony D. Barone、Martin Diggelmann、Stephen P. A. Fodor、Erik Gentalen、Nam Ngo

  DOI：10.1021/ja964427a

  日期：1997.6.1

  New methods based on photolithography and surface fluorescence were used to determine photodeprotection rates and stepwise yields for light-directed oligonucleotide synthesis using photolabile 5‘-(((α-methyl-2-nitropiperonyl)oxy)carbonyl)(MeNPOC)-2‘-deoxynucleoside phosphoramidites on planar glass substrates. Under near-UV illumination (primarily 365 nm) from a mercury light source, the rate of photoremoval

  基于光刻和表面荧光的新方法用于确定使用光不稳定 5'-(((α-methyl-2-nitropiperonyl)oxy)carbonyl)(MeNPOC)-2'-的光导向寡核苷酸合成的光脱保护速率和逐步产率平面玻璃基板上的脱氧核苷亚磷酰胺。在来自汞光源的近紫外线照射（主要是 365 nm）下，发现 MeNPOC 保护基团的光去除率与生长的寡聚体的核苷酸和长度无关（t1/2 = 12 s，27.5 mW /cm2）。观察到对溶剂极性的适度依赖性，在存在非极性溶剂或不存在溶剂的情况下，光解进行得最快（例如，t1/2 = 10-13 s，27.5 mW/cm2）。在解决方案中，光解速率在 5-50 mW/cm2 范围内与光强度呈线性关系。使用基于 N6-(苯氧基乙酰基)-2'-脱氧腺苷的单体合成十二聚体寡核苷酸的平均逐步产率在 92-94% 的范围内。
• New Photolabile Protecting Groups in Nucleoside and Nucleotide Chemistry—Synthesis, Cleavage Mechanisms and Applications
  作者：H. Giegrich、S. Eisele-Bühler、Chr Hermann、E. Kvasyuk、R. Charubala、W. Pfleiderer

  DOI：10.1080/07328319808004738

  日期：1998.9

  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.