[²H₄]pyridine | 92573-93-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [²H₄]pyridine
• 英文别名: 2,3,4,5-tetradeuteriopyridine；3,4,5,6-tetradeuteriopyridine；3,4,5,6-Tetradeuteropyridin
• CAS: 92573-93-8
• 化学式: C₅H₅N
• 分子量: 83.0696
• InChiKey: JUJWROOIHBZHMG-RHQRLBAQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  氘代吡啶 在 chloro(cycloocta-1,5-diene)(1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)iridium 、 氢气 作用下， 以 氘代甲醇 为溶剂， 生成 [²H₄]pyridine
  参考文献：
  名称：

  The Feasibility of Formation and Kinetics of NMR Signal Amplification by Reversible Exchange (SABRE) at High Magnetic Field (9.4 T)

  摘要：

  H-1 NMR signal amplification by reversible exchange (SABRE) was observed for pyridine and pyridine-d(s) at 9.4 T, a field that is orders of magnitude higher than what is typically utilized to achieve the conventional low-field SABRE effect. In addition to emissive peaks for the hydrogen spins at the ortho positions of the pyridine substrate (both free and bound to the metal center), absorptive signals are observed from hyperpolarized orthohydrogen and Ir-complex dihydride. Real-time kinetics studies show that the polarization buildup rates for these three species are in close agreement with their respective H-1 T-1 relaxation rates at 9.4 T. The results suggest that the mechanism of the substrate polarization involves cross-relaxation with hyperpolarized species in a manner similar to the spin-polarization induced nuclear Overhauser effect. Experiments utilizing pyridine-d(s) as the substrate exhibited larger enhancements as well as partial HID exchange for the hydrogen atom in the ortho position of pyridine and concomitant formation of HD molecules. While the mechanism of polarization enhancement does not explicitly require chemical exchange of hydrogen atoms of parahydrogen and the substrate, the partial chemical modification of the substrate via hydrogen exchange means that SABRE under these conditions cannot rigorously be referred to as a non-hydrogenative parahydrogen induced polarization process.

  DOI：

  10.1021/ja501052p

文献信息

• Synthesis of three alpha 7 agonists in labeled form
  作者：Charles S. Elmore、Scott Landvatter、Peter N. Dorff、Mark E. Powell、David Killick、Timothy Blake、James Hall、J. Richard Heys、John Harding、Rebecca Urbanek、Glen Ernst

  DOI：10.1002/jlcr.3186

  日期：2014.5.15

  In support of a program to develop an alpha 7 agonist as a treatment for Alzheimer's disease, three drug candidates, 1, 2, and 3, were prepared in labeled forms. Compound 1 was prepared in C-14 labeled form by lithiation of [2,6-14C2]2-chloropyridine and subsequent coupling with spirooxirane-2,3'-quinuclidine. When this same coupling was attempted using [3,4,5,6-2H4]2-chloropyridine, alcohol [2H6]-6 was the major product indicating that the primary isotope effect for the lithiation step was significant enough to shift the reaction pathway. Therefore, an alternate site of labeling was used to prepare [2H4]-1. [13C5]-2 was prepared in five steps from [13C5]2-furoic acid, but the C-14 labeled compound used [14C2]-1 as the starting material instead. [14C2]-3 was prepared in two steps from [carbonyl-14C]nicotinic acid.

  为了支持开发α 7激动剂作为阿尔茨海默病治疗的项目，准备了三种药物候选物，1、2和3，采用标记形式合成。化合物1通过锂化[2,6-14C2]2-氯吡啶，并随后与螺氧杂环-2,3'-奎宁结合，制备成C-14标记形式。当尝试使用[3,4,5,6-2H4]2-氯吡啶进行相同的结合时，产生了酒精[2H6]-6作为主要产物，这表明锂化步骤的主要同位素效应足够显著，以改变反应路径。因此，采用了另一种标记位点来制备[2H4]-1。[13C5]-2是通过五步从[13C5]2-呋喃酸合成的，但C-14标记的化合物则是以[14C2]-1为起始材料。[14C2]-3是通过两步从[羰基-14C]烟酸合成的。
• Synthesis and spectroscopic properties of isomeric trideuterio- and tetradeuterio pyridines
  作者：James W. Pavlik、Somchoke Laohhasurayotin

  DOI：10.1002/jhet.5570440637

  日期：2007.11

  The syntheses of the six possible isomeric trideuteriopyridines and the three possible isomeric tetradeuteriopyridines are described. These deuteriopyridines were characterized by their mass and NMR spectra.

  描述了六个可能的异构的三氘吡啶和三个可能的异构的四氘吡啶的合成。这些氘代吡啶通过它们的质量和NMR谱来表征。
• The Vapor-Phase Phototransposition Chemistry of Pyridine:  Deuterium Labeling Studies
  作者：James W. Pavlik、Somchoke Laohhasurayotin

  DOI：10.1021/jo7026799

  日期：2008.4.1

  The six isomeric trideuteriopyridines and the three isomeric tetradeuteriopyridines undergo phototransposition upon S0 → S2 (π, π*) excitation in the vapor phase at 254 nm. On the basis of the products formed, the six trideuteriopyridine isomers can be divided into two triads. Similarly, the three isomeric tetradeuteriopyridines also constitute a triad. Irradiation of any one member of each triad results

  在254 nm的气相中，S 0 →S 2（π，π*）激发后，六个异构的三氘吡啶和三个异构的四吡啶吡啶发生光子转移。根据形成的产物，可以将六个氘代氘代吡啶的异构体分为两个三联体。同样，三个异构的四氘代吡啶也构成一个三联体。照射每个三合会的任何一个成员会导致形成该三合会的其他两个成员。这些异构化与涉及光环化，氮在环戊烯基环的五个侧面周围迁移以及重新麦芽化的机理一致。
• The Feasibility of Formation and Kinetics of NMR Signal Amplification by Reversible Exchange (SABRE) at High Magnetic Field (9.4 T)
  作者：Danila A. Barskiy、Kirill V. Kovtunov、Igor V. Koptyug、Ping He、Kirsten A. Groome、Quinn A. Best、Fan Shi、Boyd M. Goodson、Roman V. Shchepin、Aaron M. Coffey、Kevin W. Waddell、Eduard Y. Chekmenev

  DOI：10.1021/ja501052p

  日期：2014.3.5

  H-1 NMR signal amplification by reversible exchange (SABRE) was observed for pyridine and pyridine-d(s) at 9.4 T, a field that is orders of magnitude higher than what is typically utilized to achieve the conventional low-field SABRE effect. In addition to emissive peaks for the hydrogen spins at the ortho positions of the pyridine substrate (both free and bound to the metal center), absorptive signals are observed from hyperpolarized orthohydrogen and Ir-complex dihydride. Real-time kinetics studies show that the polarization buildup rates for these three species are in close agreement with their respective H-1 T-1 relaxation rates at 9.4 T. The results suggest that the mechanism of the substrate polarization involves cross-relaxation with hyperpolarized species in a manner similar to the spin-polarization induced nuclear Overhauser effect. Experiments utilizing pyridine-d(s) as the substrate exhibited larger enhancements as well as partial HID exchange for the hydrogen atom in the ortho position of pyridine and concomitant formation of HD molecules. While the mechanism of polarization enhancement does not explicitly require chemical exchange of hydrogen atoms of parahydrogen and the substrate, the partial chemical modification of the substrate via hydrogen exchange means that SABRE under these conditions cannot rigorously be referred to as a non-hydrogenative parahydrogen induced polarization process.