4,N-ditrityl-aniline | 186639-10-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 4,N-ditrityl-aniline
• 英文别名: 4,N-Ditrityl-anilin；N,4-ditritylaniline
• CAS: 186639-10-1
• 化学式: C₄₄H₃₅N
• 分子量: 577.769
• InChiKey: IBYUBQRYOHBBCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.6
• 重原子数：
  45
• 可旋转键数：
  9
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,N-ditrityl-aniline 以 乙腈 为溶剂， 生成 triphenylmethyl radical
  参考文献：
  名称：

  Photodissociation of N-(Triphenylmethyl)anilines:  A Laser Flash Photolysis, ESR, and Product Analysis Study¹

  摘要：

  N-(Triphenylmethyl)anilines (Ph3C-NHPh-R, R = H, o-Me, m-Me, p-Me, p-CPh3), upon photolysis with 248- and 308-nm laser light, as well as by lamp irradiation with 254-nm light in acetonitrile and hexane solutions, undergo exclusively C-N bond homolysis to give the triphenylmethyl radical in a monophotonic process. Product analysis gives as main products Ph3CH, 9-Ph-fluorene, and PhNH2. The quantum yields for the formation of Ph3C. are high (0.6-0.8, 248-nm excitation) and independent of the solvent. This effective homolytic dissociation results from the low electronegativity difference between the carbon and nitrogen atoms constituting the bond to be broken, the low bond dissociation enthalpy of the C-N bond, the high excitation energy of the local chromophore (aniline), and probably from a favorable alignment of the C-N bond in a plane perpendicular to the anilino chromophore (due to the large steric requirements of the trityl group), thus enabling an effective hyperconjugative interaction with it. The above dissociation competes effectively with heterolytic cleavage, which is the pathway dominating, e.g., in the photolysis of Ph3C-Cl in MeCN under the same conditions. At high pulse intensities the trityl radicals formed above are excited by a second photon leading to either electrocyclization to 4a,4b-dihydro-9-phenylfluorenyl radical (DHPF.), or photoionization to PhaC(+), the latter only in MeCN and only on 248-nm photolysis. A new intermediate (9-Ph-4aH-fluorene) on the way to the final product 9-Ph-fluorene is identified resulting from electrocyclization, supporting a mechanism proposed earlier. The optical measurements are supported by ESR studies (irradiation with 254-nm light).

  DOI：

  10.1021/jo9719261
• 作为产物：
  描述：

  4-三甲基苯胺 、 三苯基氯甲烷 在 吡啶 作用下， 生成 4,N-ditrityl-aniline
  参考文献：
  名称：

  Verkade et al., Recueil des Travaux Chimiques des Pays-Bas, 1952, vol. 71, p. 1007,1009

  摘要：

  DOI：

文献信息

• Verkade et al., Recueil des Travaux Chimiques des Pays-Bas, 1952, vol. 71, p. 1007,1009
  作者：Verkade et al.

  DOI：——

  日期：——
• Siskos, Michael G.; Tzerpos, Nikolaos I.; Zarkadis, Antonios K., Bulletin des Societes Chimiques Belges, 1996, vol. 105, # 12, p. 759 - 768
  作者：Siskos, Michael G.、Tzerpos, Nikolaos I.、Zarkadis, Antonios K.

  DOI：——

  日期：——
• Photodissociation of <i>N</i>-(Triphenylmethyl)anilines:  A Laser Flash Photolysis, ESR, and Product Analysis Study¹
  作者：M. G. Siskos、A. K. Zarkadis、S. Steenken、N. Karakostas、S. K. Garas

  DOI：10.1021/jo9719261

  日期：1998.5.1

  N-(Triphenylmethyl)anilines (Ph3C-NHPh-R, R = H, o-Me, m-Me, p-Me, p-CPh3), upon photolysis with 248- and 308-nm laser light, as well as by lamp irradiation with 254-nm light in acetonitrile and hexane solutions, undergo exclusively C-N bond homolysis to give the triphenylmethyl radical in a monophotonic process. Product analysis gives as main products Ph3CH, 9-Ph-fluorene, and PhNH2. The quantum yields for the formation of Ph3C. are high (0.6-0.8, 248-nm excitation) and independent of the solvent. This effective homolytic dissociation results from the low electronegativity difference between the carbon and nitrogen atoms constituting the bond to be broken, the low bond dissociation enthalpy of the C-N bond, the high excitation energy of the local chromophore (aniline), and probably from a favorable alignment of the C-N bond in a plane perpendicular to the anilino chromophore (due to the large steric requirements of the trityl group), thus enabling an effective hyperconjugative interaction with it. The above dissociation competes effectively with heterolytic cleavage, which is the pathway dominating, e.g., in the photolysis of Ph3C-Cl in MeCN under the same conditions. At high pulse intensities the trityl radicals formed above are excited by a second photon leading to either electrocyclization to 4a,4b-dihydro-9-phenylfluorenyl radical (DHPF.), or photoionization to PhaC(+), the latter only in MeCN and only on 248-nm photolysis. A new intermediate (9-Ph-4aH-fluorene) on the way to the final product 9-Ph-fluorene is identified resulting from electrocyclization, supporting a mechanism proposed earlier. The optical measurements are supported by ESR studies (irradiation with 254-nm light).