N-benzylideneethan-1-ideiminium | 92314-62-0

• 英文名称: N-benzylideneethan-1-ideiminium
• CAS: 92314-62-0
• 化学式: C₉H₉N
• 分子量: 131.177
• InChiKey: NQBLHMPODFVSMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  3-methyl-2-phenyl-2H-azirine 以 氘代乙腈 为溶剂， 反应 16.0h， 生成 N-benzylideneethan-1-ideiminium
  参考文献：
  名称：

  3-甲基-2-苯基-2H-嗪的单线态光反应性

  摘要：

  在氩气基质中于254 nm处辐射3-甲基-2-苯基-2 H-叠氮基（1）产生叶立德6。类似地，在乙腈中 对叠氮基1进行激光快速光解（λ = 266 nm），得到内鎓盐6，其具有约340 nm的λmax的瞬时吸收和14μs的寿命。进行密度泛函理论计算以支持溶液和氩气基质中叶立德6的表征。氮杂环丙烯的照射1大于300nm先前已报道（有机化学杂志。2014 （79，653）在溶液中产生三重态乙烯基硝烯，在低温氩气基质中产生酮亚胺。因此，叠氮化物1的光化学取决于照射波长。

  DOI：

  10.1071/ch16604

文献信息

• Carbonyl ylides photogenerated from isomeric stilbene oxides. Temperature dependence of decay kinetics
  作者：C. V. Kumar、S. K. Chattopadhyay、P. K. Das

  DOI：10.1021/j150667a036

  日期：1984.11
• Laser Flash Photolysis Study of Phenylcarbene and Pentafluorophenylcarbene
  作者：Atnaf Admasu、Anna Dóra Gudmundsdóttir、Matthew S. Platz

  DOI：10.1021/jp963332s

  日期：1997.5.1

  Laser flash photolysis (LFP) (XeCl, 308 nm, 17 ns) of phenyldiazomethane and pentafluorophenyldiazomethane releases phenylcarbene (PC) and pentafluorophenylcarbene (PFPC), respectively. In acetonitrile solvent the carbenes react rapidly to form nitrile ylides which have convenient absorption maxima for optical detection (lambda(max)=350 nm). Phenylcarbene and pentafluorophenylcarbene each react with acetonitrile with an absolute rate constant of 2.4x10(6) M-1 s(-1) in CF2ClCFCl2 (Freon-113) at ambient temperature. The lifetimes of spin-equilibrated PC and PFPC are 190 and 500 ns in Freon-113, respectively. and the lifetime of each carbene is deduced to be 22 ns in neat acetonitrile. LFP of phenyl and pentafluorophenyldiazomethane in the presence of pyridine leads to the expected pyridine ylide. The observed absolute rate constants of reaction of spin equilibrated PC and PFPC with pyridine are 1.9 x 10(7) and 5.1 x 10(7) M-1 s(-1), respectively, in Freon-113 at ambient temperature. From this data, one can deduce singlet-triplet splittings (Delta G(ST), 298 K) of 2.3 and 3.1 kcal/mol for PC and PFPC, respectively, which is the difference in energy between the triplet minimum and the point of intersection of the singlet and triplet carbene plus pyridine surfaces. LFP of phenyldiazomethane and pentafluorophenyldiazomethane in acetonitrile containing carbene scavengers (e.g., alcohols, alkenes, and silanes) gives reduced yields of nitrile ylides. Analysis of the yield of ylide as a function of quencher by the Stern-Volmer method gives k(Q) tau values of carbene quenching. Low-temperature (77 K) photolysis of pentafluorophenyldiazomethane generates the persistent EPR spectrum of triplet pentafluorophenylcarbene which is the ground state of this carbene. However, photolysis of pentafluorophenyldiazomethane at ambient temperature generates stable reaction products derived from capture of singlet pentafluorophenylcarbene. Thus the properties of pentafluorophenylcarbene are remarkably similar to those of phenylcarbene. Each carbene has a triplet ground state but reacts in solution at ambient temperature through a low-lying excited singlet state. The lack of a fluorine substituent effect on the behavior of phenylcarbene is compared to that in singlet phenylnitrene.