| 259821-04-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• CAS: 259821-04-0
• 化学式: C₂₄H₂₇N₅O₂S
• 分子量: 449.577
• InChiKey: RCOSPAVEUWEDOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  32.0
• 可旋转键数：
  11.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  82.91
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  在 盐酸 、 18-冠醚-6 、 potassium tert-butylate 、 水 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 2.0h， 生成 6,6'-(4-(propylthio)pyridine-2,6-diyl)bis(4-(6-(6-(6-(6-(1-ethoxyvinyl)pyrimidin-4-yl)-4-(propylthio)pyridin-2-yl)pyrimidin-4-yl)-4-(propylthio)pyridin-2-yl)pyrimidine)
  参考文献：
  名称：

  Helicity Coding: Programmed Molecular Self-Organization of Achiral Nonbiological Strands into Multiturn Helical Superstructures: Synthesis and Characterization of Alternating Pyridine-Pyrimidine Oligomers

  摘要：

  Alternating pyridine-pyrimidine oligomers 1, 2, and 3, composed of nineteen, twenty one, and twenty seven heterocycles, respectively, have been synthesized in stepwise fashion and characterized. Examination of their H-1 NMR spectra revealed that these achiral nonbiological oligomers organize spontaneously into multiturn helical structures 1A-3A in solution, as indicated by marked upfield shifts of the aromatic protons coupled with distinct NOE effects. In view of their potential electron-acceptor properties compounds 1-3 also represent coiled wires of nanometric lengths, up to about 90 Angstrom for 3 in its extended form. The helical structure has been confirmed for 1 in the solid state by X-ray crystallography; a chiral channel arrangement involving only one helical enantiomer was found despite of the lack of chiral center in the strand. The oligomers exhibit a broad structureless fluorescence with a large Stokes shift, attributable to intramolecular pyridine excimer emission resulting from the helical ordering. Variable-temperature H-1 NMR experiments revealed that the oligomers exist as equilibrating mixtures of right-handed and left-handed helices. The barrier for helical handedness reversal was found to be independent on the length of the strand; two- (6), three- (1), and four-turn (3) helices showed comparable free energies of activation. Based on these observations, a stepwise folding mechanism involving two perpendicularly twisted pyridine-pyrimidine units in the transition states may be proposed for the helicity inversion processes. The present results together with earlier work indicate that the pyridine-pyrimidine sequence may be considered as a helicity codon, enforcing the formation of helical structures on the basis of: intramolecular structural information.

  DOI：

  10.1002/(sici)1521-3765(19991203)5:12<3471::aid-chem3471>3.0.co;2-5
• 作为产物：
  描述：

  4-acetyl-6-(1-ethoxyvinyl)pyrimidine 在 18-冠醚-6 、 potassium tert-butylate 、 sodium hydride 、 二甲基亚砜 作用下， 以 四氢呋喃 为溶剂， 反应 38.83h， 生成
  参考文献：
  名称：

  Helicity Coding: Programmed Molecular Self-Organization of Achiral Nonbiological Strands into Multiturn Helical Superstructures: Synthesis and Characterization of Alternating Pyridine-Pyrimidine Oligomers

  摘要：

  Alternating pyridine-pyrimidine oligomers 1, 2, and 3, composed of nineteen, twenty one, and twenty seven heterocycles, respectively, have been synthesized in stepwise fashion and characterized. Examination of their H-1 NMR spectra revealed that these achiral nonbiological oligomers organize spontaneously into multiturn helical structures 1A-3A in solution, as indicated by marked upfield shifts of the aromatic protons coupled with distinct NOE effects. In view of their potential electron-acceptor properties compounds 1-3 also represent coiled wires of nanometric lengths, up to about 90 Angstrom for 3 in its extended form. The helical structure has been confirmed for 1 in the solid state by X-ray crystallography; a chiral channel arrangement involving only one helical enantiomer was found despite of the lack of chiral center in the strand. The oligomers exhibit a broad structureless fluorescence with a large Stokes shift, attributable to intramolecular pyridine excimer emission resulting from the helical ordering. Variable-temperature H-1 NMR experiments revealed that the oligomers exist as equilibrating mixtures of right-handed and left-handed helices. The barrier for helical handedness reversal was found to be independent on the length of the strand; two- (6), three- (1), and four-turn (3) helices showed comparable free energies of activation. Based on these observations, a stepwise folding mechanism involving two perpendicularly twisted pyridine-pyrimidine units in the transition states may be proposed for the helicity inversion processes. The present results together with earlier work indicate that the pyridine-pyrimidine sequence may be considered as a helicity codon, enforcing the formation of helical structures on the basis of: intramolecular structural information.

  DOI：

  10.1002/(sici)1521-3765(19991203)5:12<3471::aid-chem3471>3.0.co;2-5