2,7-di-t-butyl-1-nitropyrene | 88829-56-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 2,7-di-t-butyl-1-nitropyrene
• 英文别名: 2,7-DI-Tert-butyl-1-nitropyrene；2,7-ditert-butyl-1-nitropyrene
• CAS: 88829-56-5
• 化学式: C₂₄H₂₅NO₂
• 分子量: 359.468
• InChiKey: LIQPHRZQGMLRHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,7-di-t-butyl-1-nitropyrene 在 sodium amalgam 、 三乙胺 作用下， 以 甲醇 为溶剂， 生成 N-<(4-Nitrophenyl)thio>-2,7-di-tert-butyl-1-aminopyrene
  参考文献：
  名称：

  Preparation and Isolation of an Exceptionally Persistent Nitrogen-centered Free Radical.N-[(4-Nitrophenyl)thio]-2.7-di-t-butyl-1-pyrenylaminyl

  摘要：

  N-[(4-硝基苯基)硫基]-2,7-二叔丁基-1-氨基芘的氧化产生异常持久且对氧不敏感的 N-[(4-硝基苯基)硫基]-2,7-二-t-丁基-1-芘基氨基，以纯自由基晶体形式分离出来，产率 31%。晶体可以长期保存而不分解。

  DOI：

  10.1246/cl.1992.1831
• 作为产物：
  描述：

  2,7-二叔丁基芘 在 硝酸 作用下， 以 溶剂黄146 为溶剂， 以75%的产率得到2,7-di-t-butyl-1-nitropyrene
  参考文献：
  名称：

  2-叔丁基-硝基py和2,7-二叔丁基-1-硝基py，在空间上严重阻碍芳族硝基化合物

  摘要：

  将2-叔丁基py和2,7-二叔丁基py硝化会生成硝基衍生物，该硝基衍生物显示出硝基与芳族π系统之间的相互作用非常弱。硝基的取向阻止该基团与π-系统共轭，导致pyr电子光谱不受干扰。

  DOI：

  10.1039/c39830001039

文献信息

• 2-t-Butyl-nitropyrene and 2,7-di-t-butyl-1-nitropyrene, sterically severely hindered aromatic nitro compounds
  作者：Leon Rodenburg、Renze Brandsma、Cees Tintel、Jan Cornelisse、Johan Lugtenburg

  DOI：10.1039/c39830001039

  日期：——

  Nitration of 2-t-Butylpyrene and 2,7-di-t-butylpyrene leads to nitro derivatives which show an extremely weak interaction between the nitro group and the aromatic π-system; the orientation of the nitro group prevents this group from conjugation with the π-system, leading to an unperturbed pyrene electronic spectrum.

  将2-叔丁基py和2,7-二叔丁基py硝化会生成硝基衍生物，该硝基衍生物显示出硝基与芳族π系统之间的相互作用非常弱。硝基的取向阻止该基团与π-系统共轭，导致pyr电子光谱不受干扰。
• Preparation and Isolation of an Exceptionally Persistent Nitrogen-centered Free Radical.<i>N</i>-[(4-Nitrophenyl)thio]-2.7-di-<i>t</i>-butyl-1-pyrenylaminyl
  作者：Yozo Miura、Eiji Yamano、Akio Tanaka、Yoshiaki Ogo

  DOI：10.1246/cl.1992.1831

  日期：1992.9

  Oxidation of N-[(4-nitrophenyl)thio]-2,7-di-t-butyl-1-aminopyrene yields an exceptionally persistent and oxygen-insensitive N-[(4-nitrophenyl)thio]-2,7-di-t-butyl-1-pyrenylaminyl, which has been isolated as pure radical crystals in 31% yield. The crystals can be stored, without decomposition, for a long period.

  N-[(4-硝基苯基)硫基]-2,7-二叔丁基-1-氨基芘的氧化产生异常持久且对氧不敏感的 N-[(4-硝基苯基)硫基]-2,7-二-t-丁基-1-芘基氨基，以纯自由基晶体形式分离出来，产率 31%。晶体可以长期保存而不分解。
• Further insight via 15N NMR spectroscopy into the reactive intermediates formed by superacid protonation of crowded nitro-PAHs: persistent dihydroxyiminiumpyrenium and hydroxyiminiumpyrenium dications
  作者：Kenneth K. Laali、Poul Erik Hansen

  DOI：10.1039/a800208h

  日期：——

  FSO3H·SbF5 (4∶1)–SO2ClF generates either the dihydroxyiminiumpyrenium dication (NO2 diprotonation) or the hydroxyiminiumpyrenium dication as the principle NMR observable persistent species (depending on the sample concentration, reaction time and the superacid). The latter is independently generated by diprotonation of authentic 1-nitrosopyrene. Variable formation of dihydroxyiminiumpyrenium and hydroxyiminiumpyrenium

  用FSO 3 H·SbF 5（1∶1）（'magic acid'）– SO 2 ClF（或SO 2）或FSO 3 H·SbF 5（1：1）进行1-硝基py及其15 N标记的同位素异构体的低温质子化41：1）–SO 2 ClF生成二羟基亚胺基吡啶鎓指示剂（NO 2双质子化）或羟基亚胺基吡啶鎓作为NMR可观察到的主要持久性物质（取决于样品浓度，反应时间和超强酸）。后者是由真实的1-亚硝基op的双质子化反应独立产生的。在空间拥挤的1-硝基-2,7-二叔丁基py的质子化中还观察到了二羟基亚胺吡啶鎓和羟基亚胺鎓吡啶鎓盐的可变形成，这在FSO 3 H·SbF 5（1∶1）–SO中给出了相应的二羟基亚铵吡啶鎓盐。与FSO 3 H·SO 2 ClF或CF 3 SO低温反应制得2 ClF（或SO 2）和羟基亚胺基py3 H·SO 2。所述挟着1-硝基2,4,6,8,10-pentaisopropylpyrene及其质子化15
• Rodenburg, L.; Brandsma, R.; Tintel, C., Recueil des Travaux Chimiques des Pays-Bas, 1986, vol. 105, # 5, p. 156 - 161
  作者：Rodenburg, L.、Brandsma, R.、Tintel, C.、Thuijl, J. van、Lugtenburg, J.、Cornelisse, J.

  DOI：——

  日期：——
• Mono- and di-nitroalkyl-(cycloalkyl-)pyrenes in superacid media: dihydroxyiminium-(oxoiminium-)pyrenium dications; cyclisation to long-lived oxazoline-(and 1,2-oxazine-)pyrenium ions, ring opening to form nitrosoalkylpyrenium and nitroso radical cation salts with unprecedented stability
  作者：Kenneth K. Laali、Simon Bolvig、Poul Erik Hansen

  DOI：10.1039/p29950000537

  日期：——

  The low temperature protonations of sterically crowded molecules 2,4,6,8,10-pentaisopropyl-1-nitropyrene 1, 2,4,6,8,10-pentaisopropyl-1,3-dinitropyrene 12, 3,6,8,10-tetracyclohexyl-1-nitropyrene 16, 2,7-di-tert-butyl-1-nitropyrene 19, 2,7-di-tert-butyl-1,8-dinitropyrene 21, 1,3,6,8-tetraisopropyl-4-nitropyrene 23 and parent 1-nitropyrene 28, all possessing buttressed nitro groups, were studied in various superacid media under persistent ion conditions. Nitro group diprotonation was observed in all cases to give N,N-dihydroxyiminium-pyrenium (or oxoiminium-pyrenium) dications. The resulting dications derived from 1, 12, 16 and 23 undergo a facile intramolecular nitro group yclisation (which is usually complete within minutes at -75 degrees C --> room temp.) to give oxazoline-(or oxazine-)pyrenium cations 6 (and 11), 14 (and 15), 18 and 25. The charge distribution patterns (probed by C-13 and H-1 chemical shift analysis) for the iminium-pyrenium dications and their cyclised derivatives illustrate extensive charge delocalisation away from the iminium group at the alternating carbons of the periphery, similar to alkylpyrenium and fluoro(alkyl) pyrenium ions. The remote a positions carry substantial positive charge, which increases with the presence of inductively stabilising alkyl (cycloalkyl) substituents. The assignment of the iminium carbon was proved by independent synthesis and protonation of the 15-N labelled 1. Quenching of 6, 18 and 14 (containing 15) does not furnish their N-hydroxyoxazoline derivatives (like 5) nor the alkylnitropyrene precursors. Instead, the corresponding nitroso-alkylpyrenium and its derived radical cation salts (like 9a and 9RC) are obtained (EPR), which when re-dissolved in (CFSOH)-S-3-H-3 or (FSOH)-H-3 reform the cyclised pyrenium ions. Formation of persistent radical cations was also detected in some cases upon storage of the nitroalkylpyrene samples in (CFSOH)-S-3-H-3 ('TfOH') at room temperature.Ring opening of 25 and reduction upon quenching produces a different type of persistent nitrosoalkylpyrene radical (27 <-> 27a) with smaller a(N). The mechanistic aspects of nitro group cyclisation/ring opening are discussed.