5-cyclopropyl-2,4-bis(trimethylsilyloxy)pyrimidine | 59968-56-8

• 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-cyclopropyl-2,4-bis(trimethylsilyloxy)pyrimidine
• 英文别名: bis(trimethylsilyl)-5-cyclopropyluracil；5-Cyclopropyl-2,4-bis(trimethylsilyloxy)pyrimidin；5-cyclopropyl-2,4-bis-trimethylsilanyloxy-pyrimidine；Pyrimidine, 5-cyclopropyl-2,4-bis[(trimethylsilyl)oxy]-；(5-cyclopropyl-2-trimethylsilyloxypyrimidin-4-yl)oxy-trimethylsilane
• CAS: 59968-56-8
• 化学式: C₁₃H₂₄N₂O₂Si₂
• 分子量: 296.517
• InChiKey: HASXTSGBBYQLIA-UHFFFAOYSA-N

物化性质

• 沸点：
  313.1±44.0 °C(Predicted)
• 密度：
  1.024±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 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-cyclopropyl-2,4-bis(trimethylsilyloxy)pyrimidine 反应 12.0h， 生成 1-<3-(thym-1-yl)propyl>-5-cyclopropyluracil
  参考文献：
  名称：

  Free Radical Rearrangements in Uracil Derivatives

  摘要：

  As part of an effort to develop general probes for radical reactions involving DNA bases, several uracil derivatives were synthesized. The rates of the cyclopropyl carbinyl rearrangement in these systems were evaluated by means of competition experiments. The results indicate that when a cyclopropyl group is substituted in the 5-position of uracil, the rearrangement occurs very slowly-with a rate constant of <2.5 x 10(4) s(-1). On the other hand, the analog of the 5-hexenyl radical cyclization onto the 5,6-double bond of uracil derivatives occurs with rates which were similar to the parent process: (4.0-8.9) x 10(4) s(-1). The experimental results along with semiempirical calculations show that radicals 23 and 25 are unusually stable species. These results explain why no rearrangements are observed when a cyclopropyl-substituted thymine dimer is cleaved by reductive single electron transfer.

  DOI：

  10.1021/jo00096a021
• 作为产物：
  描述：

  环丙乙酸 在 吡啶 、 正丁基锂 、 草酰氯 、 N-环己基异丙基胺 、 N,N-二甲基甲酰胺 、 氯乙酸 作用下， 以 水 、 苯 为溶剂， 反应 4.75h， 生成 5-cyclopropyl-2,4-bis(trimethylsilyloxy)pyrimidine
  参考文献：
  名称：

  Free Radical Rearrangements in Uracil Derivatives

  摘要：

  As part of an effort to develop general probes for radical reactions involving DNA bases, several uracil derivatives were synthesized. The rates of the cyclopropyl carbinyl rearrangement in these systems were evaluated by means of competition experiments. The results indicate that when a cyclopropyl group is substituted in the 5-position of uracil, the rearrangement occurs very slowly-with a rate constant of <2.5 x 10(4) s(-1). On the other hand, the analog of the 5-hexenyl radical cyclization onto the 5,6-double bond of uracil derivatives occurs with rates which were similar to the parent process: (4.0-8.9) x 10(4) s(-1). The experimental results along with semiempirical calculations show that radicals 23 and 25 are unusually stable species. These results explain why no rearrangements are observed when a cyclopropyl-substituted thymine dimer is cleaved by reductive single electron transfer.

  DOI：

  10.1021/jo00096a021

文献信息

• Synthesis of 5-cyclopropyluracil and 5-cyclopropylcytosine by the Pd(0)-catalyzed coupling reaction
  作者：Dan Peters、Anna-Britta Hörnfeldt、Salo Gronowitz

  DOI：10.1002/jhet.5570280629

  日期：1991.10

  5-Cyclopropyluracil and cyclopropylcytosine were prepared by the Pd(0)-catalyzed coupling reaction of 5-bromo-2,4-di(trimethylsilyloxy)pyrimidine and 5-bromo-2,4-O,N-bis-trimethylsilylcytosine with tributylstan-nylcyclopropane. The reactions also gave dehalogenated pyrimidine bases as by-products. Attempts to use 2,4-O,N-bis-trimethylsilyl-5-iodocytosine as the halide gave complete dehalogenation.

  5-环丙基尿嘧啶和环丙基胞嘧啶是通过Pd（0）催化的5-溴-2,4-二（三甲基甲硅烷氧基）嘧啶与5-溴-2,4- O，N-双-三甲基甲硅烷基胞嘧啶与三丁基锡的偶合反应制备的乙烯基环丙烷。反应还产生了脱卤的嘧啶碱作为副产物。尝试使用2，4 - O，N-双-三甲基甲硅烷基-5-碘胞嘧啶作为卤化物可以完全脱卤。
• 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.
• 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.
• Basnak, Ivan; Farkas, Jiri; Zajicek, Jaroslav, Collection of Czechoslovak Chemical Communications, 1986, vol. 51, # 8, p. 1764 - 1771
  作者：Basnak, Ivan、Farkas, Jiri、Zajicek, Jaroslav、Havlas, Zdenek

  DOI：——

  日期：——
• Free Radical Rearrangements in Uracil Derivatives
  作者：David J. Fenick、Daniel E. Falvey

  DOI：10.1021/jo00096a021

  日期：1994.8

  As part of an effort to develop general probes for radical reactions involving DNA bases, several uracil derivatives were synthesized. The rates of the cyclopropyl carbinyl rearrangement in these systems were evaluated by means of competition experiments. The results indicate that when a cyclopropyl group is substituted in the 5-position of uracil, the rearrangement occurs very slowly-with a rate constant of <2.5 x 10(4) s(-1). On the other hand, the analog of the 5-hexenyl radical cyclization onto the 5,6-double bond of uracil derivatives occurs with rates which were similar to the parent process: (4.0-8.9) x 10(4) s(-1). The experimental results along with semiempirical calculations show that radicals 23 and 25 are unusually stable species. These results explain why no rearrangements are observed when a cyclopropyl-substituted thymine dimer is cleaved by reductive single electron transfer.