5-tert-butyl-2,4-bis-trimethylsilanyloxy-pyrimidine | 51223-61-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 5-tert-butyl-2,4-bis-trimethylsilanyloxy-pyrimidine
• 英文别名: (5-Tert-butyl-2-trimethylsilyloxypyrimidin-4-yl)oxy-trimethylsilane
• CAS: 51223-61-1
• 化学式: C₁₄H₂₈N₂O₂Si₂
• 分子量: 312.56
• InChiKey: SOTBCDJPBQBHLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-tert-butyl-2,4-bis-trimethylsilanyloxy-pyrimidine 在 sodium methylate 作用下， 以 甲醇 、 氯仿 为溶剂， 生成 5-叔丁基-2'-脱氧尿苷
  参考文献：
  名称：

  The Synthesis of Some 5-Substituted and 5,6-Disubstituted 2′-Deoxyuridines

  摘要：

  5-Alkyl(cycloalkyl)-2'-deoxyuridines VIa-VIf were synthesised in high yields by condensation of the corresponding silylated bases with 2-deoxy-3,5-di-O-p-toluoyl-D-erythro-pentosyl chloride in chloroform and subsequent deblocking with sodium methoxide in methanol. The beta-configuration, anti-glycosidic conformation and C2'-endo (S) sugar pucker of all of these compounds has been established from their H-1 NMR, C-13 NMR, UV and mass spectra. Under the same conditions, the condensation of silylated 5,6-trimethyleneuracil, resulted in 1:2/alpha:beta anomeric mixture (overall yield 71%) and syn-conformation of the 5,6-trimethylene-2'-deoxyuridine [Xg]. The results of the condensation of the silylated 5,6-dimethyluracil are discussed as well. No significant antiviral activity has been found in testing the synthesised compounds against a range of herpes, influenza and HIV-1 viruses.

  DOI：

  10.1080/15257779408013234
• 作为产物：
  描述：

  叔丁乙酸甲酯 在 氯乙酸 、 六甲基二硅氮烷 、 lithium diisopropyl amide 作用下， 以 水 为溶剂， 反应 12.0h， 生成 5-tert-butyl-2,4-bis-trimethylsilanyloxy-pyrimidine
  参考文献：
  名称：

  The Synthesis of Some 5-Substituted and 5,6-Disubstituted 2′-Deoxyuridines

  摘要：

  5-Alkyl(cycloalkyl)-2'-deoxyuridines VIa-VIf were synthesised in high yields by condensation of the corresponding silylated bases with 2-deoxy-3,5-di-O-p-toluoyl-D-erythro-pentosyl chloride in chloroform and subsequent deblocking with sodium methoxide in methanol. The beta-configuration, anti-glycosidic conformation and C2'-endo (S) sugar pucker of all of these compounds has been established from their H-1 NMR, C-13 NMR, UV and mass spectra. Under the same conditions, the condensation of silylated 5,6-trimethyleneuracil, resulted in 1:2/alpha:beta anomeric mixture (overall yield 71%) and syn-conformation of the 5,6-trimethylene-2'-deoxyuridine [Xg]. The results of the condensation of the silylated 5,6-dimethyluracil are discussed as well. No significant antiviral activity has been found in testing the synthesised compounds against a range of herpes, influenza and HIV-1 viruses.

  DOI：

  10.1080/15257779408013234

文献信息

• Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
  作者：Ofelia R. Alzueta、M. Consuelo Cuquerella、Miguel A. Miranda

  DOI：10.1021/acs.joc.9b01423

  日期：2019.11.1

  triplet energy transfer is the rate controlling step, (b) excited state cyclization is the rate controlling step, and (c) the rate controlling step switches along the reaction. Thus, by introducing variations in the substitution at C5, the length of the linking bridge, or the substrate concentration, it is possible to switch from a process governed by the intrinsic dimerization step to an energy transfer-controlled

  聚亚甲基连接的联嘧啶模型已设计为具有不同的C5取代基和桥长度。用联嘧啶模型选择性辐照2'-甲氧基苯乙酮（2M），即使存在庞大的取代基也能得到环丁烷嘧啶二聚体。C5处的取代影响嘧啶（Pyr）的相对三重态能量（ET（rel））以及分子间能量转移和分子内三重态Pyr *猝灭的空间位阻。光物理研究表明，烷基取代导致ET（rel）值显着降低。证明了Pyr衍生物对2M的三重激发态的猝灭，并建立了它们的猝灭速率常数（kq）。作为一般趋势，含胸腺嘧啶的化合物的kq值高于109 M-1 s-1，而在尿嘧啶和叔丁基尿嘧啶类似物中，kq显着降低。这些数据是在三种不同的情况下进行解释的：（a）三重态能量转移是速率控制步骤，（b）激发态环化是速率控制步骤，并且（c）速率控制步骤随反应而变化。因此，通过在C5处的取代，连接桥的长度或底物浓度上引入变化，可以从由固有二聚化步骤控制的过程切换至能量转移控制的过程。
• The Synthesis of Some 5-Alkyl (Cycloalkyl)-Substituted 2′ -Deoxy-4′-Thiouridines
  作者：I. Basnak、M. Sun、P. L. Coe、R. T. Walker

  DOI：10.1080/07328319608002375

  日期：1996.1

  The silylated pyrimidine bases IIa-d were condensed with the benzyl 3,5-di-O-benzyl-2-deoxy-1,4-ditkio-D-erythro-pentofuranoside III in acetonitrile under activation by N-iodosuccinimide, giving ca 1.5 : 1/alpha: beta anomeric mixtures of the blocked nucleosides IVa-d and Va-d. in yields of 55-88%. After the separation on a silica column the pure anomers were deprotected by BCl3 or TiCl4, providing the free nucleosides VIa-d and VIIa,c,d in moderate to good overall yields. The beta- or alpha-anomeric configuration, anti-glycosidic conformation and prevailing C2'-endo(S) thiosugar pucker in the synthesized compounds were established by the combined use of the H-1, C-13 NMR and X-ray crystallography.
• The Synthesis of Some 5-Substituted and 5,6-Disubstituted 2′-Deoxyuridines
  作者：I. Basnak、A. Balkan、P. L. Coe、R. T. Walker

  DOI：10.1080/15257779408013234

  日期：1994.3

  5-Alkyl(cycloalkyl)-2'-deoxyuridines VIa-VIf were synthesised in high yields by condensation of the corresponding silylated bases with 2-deoxy-3,5-di-O-p-toluoyl-D-erythro-pentosyl chloride in chloroform and subsequent deblocking with sodium methoxide in methanol. The beta-configuration, anti-glycosidic conformation and C2'-endo (S) sugar pucker of all of these compounds has been established from their H-1 NMR, C-13 NMR, UV and mass spectra. Under the same conditions, the condensation of silylated 5,6-trimethyleneuracil, resulted in 1:2/alpha:beta anomeric mixture (overall yield 71%) and syn-conformation of the 5,6-trimethylene-2'-deoxyuridine [Xg]. The results of the condensation of the silylated 5,6-dimethyluracil are discussed as well. No significant antiviral activity has been found in testing the synthesised compounds against a range of herpes, influenza and HIV-1 viruses.