1-(¹⁵N)naphthylamine | 113511-83-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(¹⁵N)naphthylamine
• 英文别名: 1-(¹⁵N)-aminonaphthalene；<¹⁵N>-Naphthylamin；15N-α-Naphthylamin；1-<15-N>-Aminonaphthalin；naphthalen-1-yl[¹⁵N]amine；<15N>-1-Naphthylamin；naphthalen-1-(15N)amine
• CAS: 113511-83-4
• 化学式: C₁₀H₉N
• 分子量: 144.181
• InChiKey: RUFPHBVGCFYCNW-KHWBWMQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(¹⁵N)naphthylamine 在 三乙胺 、 二溴三苯基膦 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 2.75h， 生成 15N-(1-naphthyl),N-(n-octadecyl)carbodiimide
  参考文献：
  名称：

  Evidence of Entropy-Driven Bistability through ¹⁵N NMR Analysis of a Temperature- and Solvent-Induced, Chiroptical Switching Polycarbodiimide

  摘要：

  The thermo- and solvo-driven chiroptical switching process observed in specific polycarbodiimides occurs in a concerted fashion with large deviations in specific optical rotation (OR) and CD Cotton effect as a consequence of varying populations of two distinct polymer conformations. These two conformations are clearly visible in the N-15 NMR and IR spectra of the N-15-labeled poly(N-15-(1-naphthyl)-N'-octadecylcarbodiimide) (Poly-3) and poly(N-15-(1-naphthyl)-N-15'-octadecylcarbodiimide) (Poly-5). Using van't Hoff analysis, the enthalpies and entropies of switching (Delta H-switching; Delta S-switching) were calculated for both Poly-3 and Poly-5 using the relative integrations of both peaks in the N-15 NMR spectra at different temperatures to measure the populations of each state. The chiroptical switching (i.e., transitioning from state A to state B) was found to be an endothermic process (positive Delta H-switching) for both Poly-3 and Poly-5 in all solvents studied, meaning the conformation correlating with the downfield chemical shift (ca. 148 ppm, state B) is the higher enthalpy state. The compensating factor behind this phenomenon has been determined to be the large increase in entropy in CHCl3 as a result of the switching. Herein, we propose that the increased entropy in the system is a direct consequence of increased disorder in the solvent as the switching occurs. Specifically, the chloroform solvent molecules are very ordered around the polymer chains due to favorable solvent-polymer interactions, but as the switching occurs, these interactions become less favorable and disorder results. The same level of solvent disorder is not achieved in toluene, causing the chiroptical switching process to occur at higher temperatures.

  DOI：

  10.1021/ja4098803
• 作为产物：
  描述：

  萘 在 硝酸钾-15N 、 硫酸 、 palladium 10% on activated carbon 、 氢气 作用下， 以 乙醇 为溶剂， 生成 1-(¹⁵N)naphthylamine
  参考文献：
  名称：

  通过电荷密度和固态 NMR 方法绘制一系列结晶邻位取代萘的 N−C 键形成图

  摘要：

  电荷密度研究和固态核磁共振 (NMR) 1 J NC耦合测量相结合，并由周期密度泛函理论 (DFT) 计算支持，用于表征从 n-π* 相互作用到亲核氮之间成键的转变原子和亲电sp 2碳原子在一系列结晶邻位取代的萘中。随着 N⋅⋅⋅C 距离的减小，由于两组之间电荷密度的增加，拉普拉斯算子急剧减小。 N⋅⋅⋅C = 1.8 Å，周期性 DFT 计算预测，异核自旋回波 NMR 测量证实，长 C−N 键 (1.60–1.65 Å) 的1 J NC耦合约为 3–6 Hz，并且N⋅⋅⋅C >2.1 Å 的1 J NC耦合为 <1 Hz。

  DOI：

  10.1002/anie.202111100

文献信息

• Evidence of Entropy-Driven Bistability through ¹⁵N NMR Analysis of a Temperature- and Solvent-Induced, Chiroptical Switching Polycarbodiimide
  作者：James F. Reuther、Bruce M. Novak

  DOI：10.1021/ja4098803

  日期：2013.12.26

  The thermo- and solvo-driven chiroptical switching process observed in specific polycarbodiimides occurs in a concerted fashion with large deviations in specific optical rotation (OR) and CD Cotton effect as a consequence of varying populations of two distinct polymer conformations. These two conformations are clearly visible in the N-15 NMR and IR spectra of the N-15-labeled poly(N-15-(1-naphthyl)-N'-octadecylcarbodiimide) (Poly-3) and poly(N-15-(1-naphthyl)-N-15'-octadecylcarbodiimide) (Poly-5). Using van't Hoff analysis, the enthalpies and entropies of switching (Delta H-switching; Delta S-switching) were calculated for both Poly-3 and Poly-5 using the relative integrations of both peaks in the N-15 NMR spectra at different temperatures to measure the populations of each state. The chiroptical switching (i.e., transitioning from state A to state B) was found to be an endothermic process (positive Delta H-switching) for both Poly-3 and Poly-5 in all solvents studied, meaning the conformation correlating with the downfield chemical shift (ca. 148 ppm, state B) is the higher enthalpy state. The compensating factor behind this phenomenon has been determined to be the large increase in entropy in CHCl3 as a result of the switching. Herein, we propose that the increased entropy in the system is a direct consequence of increased disorder in the solvent as the switching occurs. Specifically, the chloroform solvent molecules are very ordered around the polymer chains due to favorable solvent-polymer interactions, but as the switching occurs, these interactions become less favorable and disorder results. The same level of solvent disorder is not achieved in toluene, causing the chiroptical switching process to occur at higher temperatures.
• Mapping of N−C Bond Formation from a Series of Crystalline Peri‐Substituted Naphthalenes by Charge Density and Solid‐State NMR Methodologies
  作者：Gregory J. Rees、Mateusz B. Pitak、Alberth Lari、Stephen P. Day、Jonathan R. Yates、Peter Gierth、Kristian Barnsley、Mark E. Smith、Simon J. Coles、John V. Hanna、John D. Wallis

  DOI：10.1002/anie.202111100

  日期：2021.10.25

  calculations is used to characterise the transition from an n–π* interaction to bond formation between a nucleophilic nitrogen atom and an electrophilic sp2 carbon atom in a series of crystalline peri-substituted naphthalenes. As the N⋅⋅⋅C distance reduces there is a sharp decrease in the Laplacian derived from increasing charge density between the two groups at ca. N⋅⋅⋅C = 1.8 Å, with the periodic DFT

  电荷密度研究和固态核磁共振 (NMR) 1 J NC耦合测量相结合，并由周期密度泛函理论 (DFT) 计算支持，用于表征从 n-π* 相互作用到亲核氮之间成键的转变原子和亲电sp 2碳原子在一系列结晶邻位取代的萘中。随着 N⋅⋅⋅C 距离的减小，由于两组之间电荷密度的增加，拉普拉斯算子急剧减小。 N⋅⋅⋅C = 1.8 Å，周期性 DFT 计算预测，异核自旋回波 NMR 测量证实，长 C−N 键 (1.60–1.65 Å) 的1 J NC耦合约为 3–6 Hz，并且N⋅⋅⋅C >2.1 Å 的1 J NC耦合为 <1 Hz。