ortho-biphenylnitrene | 10552-15-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ortho-biphenylnitrene
• 英文别名: (2-Phenylcyclohexa-2,5-dien-1-ylidene)azanide；(2-phenylcyclohexa-2,5-dien-1-ylidene)azanide
• CAS: 10552-15-5
• 化学式: C₁₂H₉N
• 分子量: 167.21
• InChiKey: BAKNASXHELLMLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ortho-biphenylnitrene 生成 8aH-carbazole 、 2-phenylbenzazirine
  参考文献：
  名称：

  Study of the Chemistry of ortho- and para-Biphenylnitrenes by Laser Flash Photolysis and Time-Resolved IR Experiments and by B3LYP and CASPT2 Calculations

  摘要：

  The photochemistry of ortho-biphenyl azide (1a) has been studied by laser flash photolysis (LFP), with UV-vis and IR detection of the transient intermediates formed. LFP (266 nm) of la in glassy 3-methylpentane at 77 K releases singlet ortho-biphenylnitrene (1b) (lambdamax = 410 nm, tau = 59 +/- 6 ns), which under these conditions decays cleanly to the lower energy triplet state. In fluid solution at 298 K, 1b rapidly (tau < 10 ns) partitions between formation of isocarbazole (4) (lambda(max) = 430 nm, tau = 70 ns) and benzazirine (1e) (lambda(max) = 305 nm, tau = 12 ns). Isocarbazole 4 undergoes a 1,5-hydrogen shift, with k(H)/k(D) = 3.4 at 298 K to form carbazole 9 and smaller amounts of two other isocarbazoles (7 and 8). Benzazirine 1e ring-opens reversibly to azacycloheptatetraene (1f), which serves as a reservoir for singlet nitrene 1b. Azacycloheptatetraene 1f ultimately forms carbazole 9 on the millisecond time scale by the pathway 1f le --> 1b --> 4 --> 9. The energies of the transient intermediates and of the transition structures connecting them were successfully predicted by CASPT2/6-31G* calculations. The electronic and vibrational spectra of the intermediates, computed by density functional theory, support the assignment of the transient spectra, observed in the formation of 9 from 1a.

  DOI：

  10.1021/ja0351591
• 作为产物：
  描述：

  2-叠氮基联苯 以 various solvent(s) 为溶剂， 生成 ortho-biphenylnitrene
  参考文献：
  名称：

  对联苯基、邻联苯基和 1-萘基硝基阳离子的超快光谱和基质分离研究

  摘要：

  对联苯基、邻联苯基和 1-萘基叠氮化物在 HCl 存在和不存在的情况下在低温下沉积在氩气中。在没有 HCl 的情况下，观察到相应的三线态氮烯、氮杂环和双脱氢氮杂环庚烷的已知电子和振动光谱，而在 HCl 存在下，这些叠氮化物的光解产生了分配给相应氮氮阳离子的新电子光谱。对于对联苯基叠氮化物，由此产生的氮铵离子光谱与之前观察到的该物种的溶液相光谱非常相似。该阳离子的振动谱首次被记录。提供了先前未知的邻联苯基硝基阳离子和 1-萘基硝基阳离子的光谱证据。通过 CASSCF 和 CASPT2 计算很好地再现了对和邻联苯基硝基阳离子和 1-萘基硝基阳离子的光谱。通过飞秒时间分辨激光闪光光解在 88% 甲酸中的适当叠氮化物，在溶液中检测到相同的氮鎓阳离子。在溶液中记录的氮鎓阳离子的瞬态光谱与在 HCl 基质中获得的光谱非常一致。这些阳离子的形成速率等于单线态氮烯在 88% 甲酸中的衰变速率，如下所示：p-联苯（taugrowth

  DOI：

  10.1021/ja071325j

文献信息

• The Direct Detection of an Aryl Azide Excited State:  An Ultrafast Study of the Photochemistry of <i>para</i>- and <i>ortho</i>-Biphenyl Azide
  作者：Gotard T. Burdzinski、Terry L. Gustafson、John C Hackett、Christopher M. Hadad、Matthew S. Platz

  DOI：10.1021/ja054135m

  日期：2005.10.1

  Ultrafast laser flash photolysis (266 nm) of para- and ortho-biphenyl azide in acetonitrile produces azide excited states that have broad absorption bands centered at 480 nm. The para-biphenyl azide excited singlet state has a lifetime of 100 fs. The excited-state lifetime of the ortho-azide isomer is 450 +/- 150 fs. Decay of the azide excited states is accompanied by the formation of the corresponding

  乙腈中对-和邻-联苯叠氮化物的超快激光闪光光解 (266 nm) 产生叠氮化物激发态，其吸收带宽，集中在 480 nm。对联苯叠氮激发单线态的寿命为 100 fs。邻叠氮化物异构体的激发态寿命为 450 +/- 150 fs。叠氮化物激发态的衰减伴随着相应已知单线态氮烯的形成（对位，λmax = 350 nm，邻位，λmax = 400 nm）。单线态对联苯氮烯天生具有过剩的能量，并以 11 ps 的时间常数进行振动冷却，形成长寿命（tau 约为 9 ns）松弛的单线态氮烯。单线态邻联苯腈在环境温度下在乙腈中的衰变寿命为 16 ps。
• Ultrafast Spectroscopic and Matrix Isolation Studies of <i>p-</i>Biphenylyl, <i>o</i>-Biphenylyl, and 1-Naphthylnitrenium Cations
  作者：Jin Wang、Gotard Burdzinski、Zhendong Zhu、Matthew S. Platz、Claudio Carra、Thomas Bally

  DOI：10.1021/ja071325j

  日期：2007.7.1

  temperature in the presence and absence of HCl. In the absence of HCl, the known electronic and vibrational spectra of the corresponding triplet nitrenes, azirines, and didehydroazepines were observed, whereas in the presence of HCl, photolysis of these azides produces new electronic spectra assigned to the corresponding nitrenium cations. For p-biphenylyl azide the resulting spectrum of the nitrenium

  对联苯基、邻联苯基和 1-萘基叠氮化物在 HCl 存在和不存在的情况下在低温下沉积在氩气中。在没有 HCl 的情况下，观察到相应的三线态氮烯、氮杂环和双脱氢氮杂环庚烷的已知电子和振动光谱，而在 HCl 存在下，这些叠氮化物的光解产生了分配给相应氮氮阳离子的新电子光谱。对于对联苯基叠氮化物，由此产生的氮铵离子光谱与之前观察到的该物种的溶液相光谱非常相似。该阳离子的振动谱首次被记录。提供了先前未知的邻联苯基硝基阳离子和 1-萘基硝基阳离子的光谱证据。通过 CASSCF 和 CASPT2 计算很好地再现了对和邻联苯基硝基阳离子和 1-萘基硝基阳离子的光谱。通过飞秒时间分辨激光闪光光解在 88% 甲酸中的适当叠氮化物，在溶液中检测到相同的氮鎓阳离子。在溶液中记录的氮鎓阳离子的瞬态光谱与在 HCl 基质中获得的光谱非常一致。这些阳离子的形成速率等于单线态氮烯在 88% 甲酸中的衰变速率，如下所示：p-联苯（taugrowth
• Study of the Chemistry of <i>o</i><i>rtho</i>- and <i>p</i><i>ara</i>-Biphenylnitrenes by Laser Flash Photolysis and Time-Resolved IR Experiments and by B3LYP and CASPT2 Calculations
  作者：Meng-Lin Tsao、Nina Gritsan、Tammi R. James、Matthew S. Platz、David A. Hrovat、Weston Thatcher Borden

  DOI：10.1021/ja0351591

  日期：2003.8.1

  The photochemistry of ortho-biphenyl azide (1a) has been studied by laser flash photolysis (LFP), with UV-vis and IR detection of the transient intermediates formed. LFP (266 nm) of la in glassy 3-methylpentane at 77 K releases singlet ortho-biphenylnitrene (1b) (lambdamax = 410 nm, tau = 59 +/- 6 ns), which under these conditions decays cleanly to the lower energy triplet state. In fluid solution at 298 K, 1b rapidly (tau < 10 ns) partitions between formation of isocarbazole (4) (lambda(max) = 430 nm, tau = 70 ns) and benzazirine (1e) (lambda(max) = 305 nm, tau = 12 ns). Isocarbazole 4 undergoes a 1,5-hydrogen shift, with k(H)/k(D) = 3.4 at 298 K to form carbazole 9 and smaller amounts of two other isocarbazoles (7 and 8). Benzazirine 1e ring-opens reversibly to azacycloheptatetraene (1f), which serves as a reservoir for singlet nitrene 1b. Azacycloheptatetraene 1f ultimately forms carbazole 9 on the millisecond time scale by the pathway 1f le --> 1b --> 4 --> 9. The energies of the transient intermediates and of the transition structures connecting them were successfully predicted by CASPT2/6-31G* calculations. The electronic and vibrational spectra of the intermediates, computed by density functional theory, support the assignment of the transient spectra, observed in the formation of 9 from 1a.