1,2-bis(p-N,N-diethylanilinyl)acetylene | 717879-46-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,2-bis(p-N,N-diethylanilinyl)acetylene
• 英文别名: 4,4'-ethynylenebis(N,N-diethylaniline)；4-[2-[4-(diethylamino)phenyl]ethynyl]-N,N-diethylaniline
• CAS: 717879-46-4
• 化学式: C₂₂H₂₈N₂
• 分子量: 320.478
• InChiKey: KGSGPRKQJBTEFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.78
• 重原子数：
  24.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,2-bis(p-N,N-diethylanilinyl)acetylene 在 dodecamethylcarborane radical 作用下， 以 二氯甲烷 为溶剂， 反应 24.5h， 生成 (p-N,N-diethylanilinyl)pentaphenylbenzene
  参考文献：
  名称：

  Very Fast Electron Migrations within p-Doped Aromatic Cofacial Arrays Leading to Three-Dimensional (Toroidal) π-Delocalization

  摘要：

  The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H-ab) that are required for the evaluation of the activation barrier (Delta G(ET)*) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N, N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range Delta G(ET)* = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T-t > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.

  DOI：

  10.1021/ja060393n
• 作为产物：
  描述：

  N,N-diethyl-4-iodo-aniline 、 乙炔 在 palladium dichloride copper(l) iodide 、 三苯基膦 作用下， 以 二乙胺 为溶剂， 反应 3.0h， 以94%的产率得到1,2-bis(p-N,N-diethylanilinyl)acetylene
  参考文献：
  名称：

  Very Fast Electron Migrations within p-Doped Aromatic Cofacial Arrays Leading to Three-Dimensional (Toroidal) π-Delocalization

  摘要：

  The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H-ab) that are required for the evaluation of the activation barrier (Delta G(ET)*) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N, N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range Delta G(ET)* = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T-t > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.

  DOI：

  10.1021/ja060393n

文献信息

• The [2 + 2] Cycloaddition–Retroelectrocyclization and [4 + 2] Hetero-Diels–Alder Reactions of 2-(Dicyanomethylene)indan-1,3-dione with Electron-Rich Alkynes: Influence of Lewis Acids on Reactivity
  作者：Etienne J. Donckele、Aaron D. Finke、Laurent Ruhlmann、Corinne Boudon、Nils Trapp、François Diederich

  DOI：10.1021/acs.orglett.5b01598

  日期：2015.7.17

  The reaction of electrophilic 2-(dicyanomethylene)indan-1,3-dione (DCID) with substituted, electron-rich alkynes provides two classes of push-pull chromophores with interesting optoelectronic properties. The formal [2 + 2] cycloaddition-retroelectrocydclization reaction at the exocyclic double bond of DCID gives cyanobuta-1,3-dienes, and the formal [4 + 2] hetero-Diels-Alder (HDA) reaction at an enone moiety of DCID generates fused 4H-pyran heterocycles. Both products can be obtained in good yield and excellent selectivity by carefully tuning the reaction conditions; in particular, the use of Lewis acids dramatically enhances formation of the HDA adduct.
• Through-Space (Cofacial) π-Delocalization among Multiple Aromatic Centers: Toroidal Conjugation in Hexaphenylbenzene-like Radical Cations
  作者：Duoli Sun、Sergiy V. Rosokha、Jay K. Kochi

  DOI：10.1002/anie.200501005

  日期：2005.8.12
• Very Fast Electron Migrations within p-Doped Aromatic Cofacial Arrays Leading to Three-Dimensional (Toroidal) π-Delocalization
  作者：Sergiy V. Rosokha、Ivan S. Neretin、Duoli Sun、Jay K. Kochi

  DOI：10.1021/ja060393n

  日期：2006.7.1

  The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H-ab) that are required for the evaluation of the activation barrier (Delta G(ET)*) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N, N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range Delta G(ET)* = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T-t > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.