3-methyl-N-tritylaniline | 20222-31-5

• 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: 3-methyl-N-tritylaniline
• 英文别名: N-trityl-m-toluidine；N-Trityl-m-toluidin
• CAS: 20222-31-5
• 化学式: C₂₆H₂₃N
• 分子量: 349.475
• InChiKey: WSMYVLWYFHRDLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  3-methyl-N-tritylaniline 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：

  三苯基甲醇 在 4-二甲氨基吡啶 、 三乙胺 、 乙酰氯 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.0h， 生成 3-methyl-N-tritylaniline
  参考文献：
  名称：

  钯催化芳香族卤化物对苯胺的对 C−H 芳基化

  摘要：

  通过金属互变异构方法实现了苯胺与非活化芳基卤化物的选择性对-C-H芳基化。苯胺对钯催化剂的反应性从 NH 基团转移到芳环中。在四个可能的位置中，催化芳基化通过钯上的大配体与临时安装的屏蔽基团的组合专门定向到对位-C-H位置。

  DOI：

  10.1002/anie.202210009

文献信息

• Transition-Metal-Free Direct Arylation of Anilines
  作者：Tracey Pirali、Fengzhi Zhang、Anna H. Miller、Jenna L. Head、Donald McAusland、Michael F. Greaney

  DOI：10.1002/anie.201106150

  日期：2012.1.23

  Aryne arylation: A new method of direct arylation is reported for aniline substrates. The reaction uses benzyne to synthesize a variety of aminobiaryls under mild conditions (see scheme), requiring no stoichiometric metalation or transition‐metal catalysis. An ene mechanism is implicated, and conveys excellent functional group tolerance relative to metal‐mediated processes.

  芳基芳基化：据报道苯胺底物有一种直接芳基化的新方法。该反应使用苯炔在温和条件下合成各种氨基联芳基（参见方案），无需化学计量的金属化或过渡金属催化。涉及烯键机制，并相对于金属介导的过程传达了出色的官能团耐受性。
• 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).
• Palladium‐Catalyzed <i>para</i> ‐C−H Arylation of Anilines with Aromatic Halides
  作者：Dominik Lichte、Nico Pirkl、Gregor Heinrich、Sayan Dutta、Jonas F. Goebel、Debasis Koley、Lukas J. Gooßen

  DOI：10.1002/anie.202210009

  日期：2022.11.21

  arylation of anilines with non-activated aryl halides has been achieved by a metalla-tautomerism approach. The reactivity of an aniline towards a palladium catalyst was relayed from the NH group into the aromatic ring. Out of four possible positions, the catalytic arylation was directed exclusively into the para-C−H position by a bulky ligand at the palladium in combination with a temporarily installed shielding

  通过金属互变异构方法实现了苯胺与非活化芳基卤化物的选择性对-C-H芳基化。苯胺对钯催化剂的反应性从 NH 基团转移到芳环中。在四个可能的位置中，催化芳基化通过钯上的大配体与临时安装的屏蔽基团的组合专门定向到对位-C-H位置。