2,7-Di-tert-butyl-1-aminopyrene | 144597-07-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 2,7-Di-tert-butyl-1-aminopyrene
• 英文别名: 2,7-DI-Tert-butylpyren-1-amine；2,7-ditert-butylpyren-1-amine
• CAS: 144597-07-9
• 化学式: C₂₄H₂₇N
• 分子量: 329.485
• InChiKey: KOENHPAFPMACBH-UHFFFAOYSA-N

物化性质

• 沸点：
  492.8±14.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  25
• 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：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,7-Di-tert-butyl-1-aminopyrene 在 potassium carbonate 、 lead dioxide 、 三乙胺 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 N-<(4-Nitrophenyl)thio>-2,7-di-tert-butyl-1-pyrenyl-aminyl radical
  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 sodium amalgam 、 硝酸 作用下， 以 甲醇 、 溶剂黄146 为溶剂， 反应 13.0h， 生成 2,7-Di-tert-butyl-1-aminopyrene
  参考文献：
  名称：

  Generation, Isolation, and Characterization of N-(Arylthio)-7-tert-butyl- and N-(Arylthio)-2,7-di-tert-butyl-1-pyrenylaminyl Radicals

  摘要：

  N-(Arylthio)-7-tert-butyl-1-pyrenylaminyl (2) and N-[(4-nitrophenyl)thio]-2,7-di-tert-butyl-1-pyrenylaminyl radicals (3) are prepared by PbO2 oxidation of N-(arylthio)-7-tert-butyl-1-aminopyrenes and N-[(4-nitrophenyl)thio] -2,7-di-tert-butyl-1-aminopyrene, respectively, and studied by ESR and ENDOR spectroscopy. The kinetic ESR study shows that, while aminyls 2 gradually decompose in solution at room temperature, aminyl 3 is quite persistent, even in refluxing benzene, and shows no tendency to dimerize, even at low temperatures. These interesting properties of 3 permit us to isolate 3 as radical crystals in 28-31% yield. The hyperfine splitting (hfs) constants of 2 and 3, determined by ESR and ENDOR spectroscopic methods, show an extensive delocalization of the unpaired electron onto the pyrene ring. Comparison of the hfs constants of 2 and 3 shows that a more extensive delocalization of the spin into the pyrene ring takes place in 3. This is accounted for in terms of the difference in the conformations of 2 and 3.

  DOI：

  10.1021/jo00091a015

文献信息

• <i>N</i>-<i>tert</i>-Butoxy-1-aminopyrenyl Radicals. Isolation, Electronic Structure, and Magnetic Characterization¹
  作者：Yozo Miura、Nobuaki Matsuba、Rika Tanaka、Yoshio Teki、Takeji Takui

  DOI：10.1021/jo0202785

  日期：2002.12.1

  (6) free radicals were generated by the reaction of the lithium amides of the corresponding 1-aminopyrenes with tert-butyl peroxybenzoate in THF at -78 degrees C. Although 6 could not be isolated due to the gradual decomposition in solution, 4 and 5 were quite persistent and could be isolated as monomeric radical crystals. The X-ray crystallographic analyses for the isolated free radicals were successfully

  N-叔丁氧基-2,7-二叔丁基-1-吡咯烷基（4），N-叔丁氧基-2-叔丁基-1-吡咯烷基（5）和N-叔丁氧基-7相应的1-氨基amino的锂酰胺与过氧苯甲酸叔丁酯在-78℃下的THF反应生成了叔-叔丁基-1-吡喃基（6）自由基。尽管由于在溶液中逐渐分解，4和5相当持久，可以分离为单体自由基晶体。对分离出的自由基进行了X射线晶体学分析，表明N和O原子与the环几乎共面。由于存在许多磁性不等价的质子，因此4和5的ESR光谱非常复杂。因此，质子超精细偶联（hfc）常数由（1）H ENDOR / TRIPLE共振光谱法测定。为了指定the环质子的hfc常数，制备了部分氘代的自由基4-d（4），并测量了ENDOR和ESR光谱。为了讨论4和5 ab的自旋密度分布，采用DTO UBecke 3LYP方法，使用STO 6-31G基组，进行了从头算分子轨道计算。用SQUID磁力计对4和5进行磁化率测量。对
• 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。
• Generation, Isolation, and Characterization of N-(Arylthio)-7-tert-butyl- and N-(Arylthio)-2,7-di-tert-butyl-1-pyrenylaminyl Radicals
  作者：Yozo Miura、Eiji Yamano、Akio Tanaka、Jun Yamauchi

  DOI：10.1021/jo00091a015

  日期：1994.6

  N-(Arylthio)-7-tert-butyl-1-pyrenylaminyl (2) and N-[(4-nitrophenyl)thio]-2,7-di-tert-butyl-1-pyrenylaminyl radicals (3) are prepared by PbO2 oxidation of N-(arylthio)-7-tert-butyl-1-aminopyrenes and N-[(4-nitrophenyl)thio] -2,7-di-tert-butyl-1-aminopyrene, respectively, and studied by ESR and ENDOR spectroscopy. The kinetic ESR study shows that, while aminyls 2 gradually decompose in solution at room temperature, aminyl 3 is quite persistent, even in refluxing benzene, and shows no tendency to dimerize, even at low temperatures. These interesting properties of 3 permit us to isolate 3 as radical crystals in 28-31% yield. The hyperfine splitting (hfs) constants of 2 and 3, determined by ESR and ENDOR spectroscopic methods, show an extensive delocalization of the unpaired electron onto the pyrene ring. Comparison of the hfs constants of 2 and 3 shows that a more extensive delocalization of the spin into the pyrene ring takes place in 3. This is accounted for in terms of the difference in the conformations of 2 and 3.