N-methyl-2-(4-nitrophenyl)-buckminsterfulleropyrrolidine | 174278-68-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: N-methyl-2-(4-nitrophenyl)-buckminsterfulleropyrrolidine
• 英文别名: N-methyl-2-(4-nitrophenyl)-3,4-fulleropyrrolidine
• CAS: 174278-68-3
• 化学式: C₆₉H₁₀N₂O₂
• 分子量: 898.851
• InChiKey: AAJFCQIXOWXFHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17
• 重原子数：
  73
• 可旋转键数：
  1
• 环数：
  34.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  49.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-methyl-2-(4-nitrophenyl)-buckminsterfulleropyrrolidine 在 盐酸 、 tin 作用下， 以 氯仿 为溶剂， 生成 N-methyl-2-(4-aminophenyl)-bukminsterfulleropyrrolidine
  参考文献：
  名称：

  Synthesis of novel nitroso-fulleropyrrolidines

  摘要：

  Novel fulleropyrrolidines containing differently head groups (-NO2, -NH2 -NO) spaced by a long chain from the fulleropyrrolidine moiety have been synthesised and characterised. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00944-9
• 作为产物：
  描述：

  以 氯苯 为溶剂， 生成 四(二甲氨基)乙烯 、 N-methyl-2-(4-nitrophenyl)-buckminsterfulleropyrrolidine
  参考文献：
  名称：

  Linear free-energy relationship for electron-transfer processes of pyrrolidinofullerenes with tetrakis(dimethylamino)ethylene in ground and excited states

  摘要：

  吡咯烷富勒烯基态和激发三重态电子转移过程的系统研究{C60(C3H6N)R [R=H (1), p-C6H4NO2 (2), p-C6H4CHO (3), p-C6H5 (4) )、p-C6H4OMe (5)、p-C6H4NMe2 (6)]} 与四(二甲氨基)乙烯 (TDAE) 的结合已通过可见光近红外区域的稳态和瞬态吸收测量进行。对基态电子转移过程平衡的分析表明，极性溶剂中会产生自由基。通过激光闪光光解对基态电子转移反应的平衡施加扰动，观察到通过 T(C60(C3H6N)R)* 的光诱导电子转移过程。根据热力学数据和动力学数据的关系，可以评估基态的电子转移速率常数（ketG）。与极性溶剂中的平衡常数(K)相比，ketG值受取代基的影响较小； α=0.6 in Δ log ketG=α Δ log K。该α值表明基态中正向电子转移的活化能随(C60(C3H6N)R)-的热力学稳定性适度变化。通过 T(C60(C3H6N)R)* 的电子转移速率常数接近扩散控制极限，由于其高放热过程，没有表现出大的取代基效应 (α'=0)。这种线性自由能关系可以扩展到其他体系，例如T(C60(C3H6N)R)*/N,N-二甲基苯胺，从中可以获得电子转移过程的有价值的信息。

  DOI：

  10.1039/a901837i

文献信息

• Reactions of [60]Fullerene with Halides and Amino Acids to Synthesize Fulleropyrrolidines
  作者：Bo Jin、Juan Shen、Rufang Peng、Congdi Chen、Shijin Chu

  DOI：10.1002/ejoc.201402655

  日期：2014.10

  discovery of other halides – such as allyl chloride, methallyl chloride, cinnamyl chloride, propargyl bromide, ethyl bromoacetate, bromoacetonitrile, bromomethane, bromopropane and bromobutane – that could also react with [60]fullerene and amino acids to produce fulleropyrrolidines. This reaction could be an alternative to the Prato reaction for synthesizing fulleropyrrolidines when aldehydes are expensive

  研究了 [60] 富勒烯与苄基氯和氨基酸在氯苯 (PhCl) 中的反应。从这些反应中获得了带有来自相应苄基氯的 ArCH 部分的富勒吡咯烷，通过 C-Cl 键断裂。使用PhCl/DMSO代替PhCl作为溶剂显着提高了反应效率。对这些反应的详细研究导致发现了其他卤化物——如烯丙基氯、甲基烯丙基氯、肉桂酰氯、炔丙基溴、溴乙酸乙酯、溴乙腈、溴甲烷、溴丙烷和溴丁烷——它们也可以与 [60] 富勒烯和氨基反应酸生成富勒吡咯烷。当醛价格昂贵或无法从商业来源获得时，该反应可以替代普拉托反应来合成富勒吡咯烷。提出了一种可能的产物形成反应机制，包括卤化物中的 C-X 键断裂形成醛。
• 一种N-甲基-2-(4-硝基苯基)-3,4-富勒烯吡咯烷的制备方法
  申请人：黄山学院

  公开号：CN107245051A

  公开（公告）日：2017-10-13

  一种N‑甲基‑2‑(4‑硝基苯基)‑3,4‑富勒烯吡咯烷的制备方法，包括如下步骤：(1)将C60粉末溶解于非极性溶剂中得到溶液；(2)向步骤(1)所得溶液中加入肌氨酸和对硝基苯甲醛加热、回流；(3)回流结束后混合溶液冷却，除去甲苯，得到固体产物；(4)用层析色谱柱洗脱步骤(3)所得固体产物；(5)将洗脱所得产物溶液除去溶剂，洗涤，干燥得到目标产物。本发明的制备方法简单，产物纯度高、产率高。
• Solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes under high-speed vibration milling
  作者：Guan-Wu Wang、Ting-Hu Zhang、Er-Hong Hao、Li-Juan Jiao、Yasujiro Murata、Koichi Komatsu

  DOI：10.1016/s0040-4020(02)01478-3

  日期：2003.1

  The solvent-free reactions of fullerenes and N-alkylglycines with and without aldehydes (RCHO) 2a-e under high-speed vibration milling (HSVM) conditions have been investigated. Fulleropyrrolidines 4a-e (C-60(CH2N(CH3)CHR), R=H (4a), C6H5 (4b), pNO(2)-C6H5 (4c), p-CH3O-C6H4 (4d), p-(CH3)(2)N-C6H4 (4e)) were obtained in moderate yields from reactions of C-60 with aldehydes 2a-e and N-methylglycine (Prato reaction). In all these solvent-free reactions, 4a was found to be formed besides 4b-e, indicating that fullerenes can react with N-substituted glycines in the absence of aldehyde to give fulleropyrrolidines. For this novel reaction, a possible reaction mechanism involving an electron transfer process has been proposed. Intrigued by this observation, the dependence of the yield on the reagent ratio for the reaction of C-60 with paraformaldehyde and/or N-methylglycine was examined to search the optimal conditions. The reaction of C-70 with paraformaldehyde and/or N-methylglycine under HSVM conditions was also studied and was found to give the positional isomers of [70]fulleropyrrolidines. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of novel nitroso-fulleropyrrolidines
  作者：Giuseppe Vasapollo、Giuseppe Mele、Luigia Longo、Roberto Ianne、Brian G. Gowenlock、Keith G. Orrell

  DOI：10.1016/s0040-4039(02)00944-9

  日期：2002.7

  Novel fulleropyrrolidines containing differently head groups (-NO2, -NH2 -NO) spaced by a long chain from the fulleropyrrolidine moiety have been synthesised and characterised. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Linear free-energy relationship for electron-transfer processes of pyrrolidinofullerenes with tetrakis(dimethylamino)ethylene in ground and excited states
  作者：Chuping Luo、Mamoru Fujitsuka、Chun-Hui Huang、Osamu Ito

  DOI：10.1039/a901837i

  日期：——

  Systematic studies of electron-transfer processes in the ground states and excited triplet states of pyrrolidinofullerenes C60(C3H6N)R [R=H (1), p-C6H4NO2 (2), p-C6H4CHO (3), p-C6H5 (4), p-C6H4OMe (5), p-C6H4NMe2 (6)]} with tetrakis(dimethylamino)ethylene (TDAE) have been carried out by steady-state and transient absorption measurements in the visible–NIR region. Analyses of the equilibria of the electron-transfer processes in the ground states indicate that free ion radicals are produced in polar solvents. Photoinduced electron-transfer processes viaT(C60(C3H6N)R)* were observed by applying a perturbation to the equilibria of the electron-transfer reactions in the ground states by laser flash photolysis. Based on the relationship of the thermodynamic data and kinetic data, the electron-transfer rate constants in the ground states (ketG) can be evaluated. The ketG values are affected by the substituents to a smaller extent compared with the equilibrium constants (K) in polar solvents; α=0.6 in Δ log ketG=α Δ log K. This α value indicates that the activation energies of forward electron transfer in the ground states vary moderately with the thermodynamic stabilities of (C60(C3H6N)R)-. Electron-transfer rate constants viaT(C60(C3H6N)R)*, which are close to the diffusion-controlled limit, do not show a large substituent effect (α′=0), because of their highly exothermic processes. Such a linear free-energy relationship can be extended to other systems such as T(C60(C3H6N)R)*/N,N-dimethylaniline, from which valuable information for electron-transfer processes can be obtained.

  吡咯烷富勒烯基态和激发三重态电子转移过程的系统研究C60(C3H6N)R [R=H (1), p-C6H4NO2 (2), p-C6H4CHO (3), p-C6H5 (4) )、p-C6H4OMe (5)、p-C6H4NMe2 (6)]} 与四(二甲氨基)乙烯 (TDAE) 的结合已通过可见光近红外区域的稳态和瞬态吸收测量进行。对基态电子转移过程平衡的分析表明，极性溶剂中会产生自由基。通过激光闪光光解对基态电子转移反应的平衡施加扰动，观察到通过 T(C60(C3H6N)R)* 的光诱导电子转移过程。根据热力学数据和动力学数据的关系，可以评估基态的电子转移速率常数（ketG）。与极性溶剂中的平衡常数(K)相比，ketG值受取代基的影响较小； α=0.6 in Δ log ketG=α Δ log K。该α值表明基态中正向电子转移的活化能随(C60(C3H6N)R)-的热力学稳定性适度变化。通过 T(C60(C3H6N)R)* 的电子转移速率常数接近扩散控制极限，由于其高放热过程，没有表现出大的取代基效应 (α'=0)。这种线性自由能关系可以扩展到其他体系，例如T(C60(C3H6N)R)*/N,N-二甲基苯胺，从中可以获得电子转移过程的有价值的信息。