phenylcarbene | 3101-08-4

• 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: phenylcarbene
• 英文别名: benzyl radical；phenylmethanediyl；benzylidene；benzylidene radical；Phenylmethylene；5-methylidenecyclohexa-1,3-diene
• CAS: 3101-08-4
• 化学式: C₇H₆
• 分子量: 90.1246
• InChiKey: YJLSVCJDMFHEHC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  phenylcarbene 以 various solvent(s) 为溶剂， 反应 19.0h， 生成 Triplett-Cycloheptatrienyliden
  参考文献：
  名称：

  1,2,4,6-Cycloheptatetraene: the key intermediate in arylcarbene interconversions and related C7H6 rearrangements

  摘要：

  DOI：

  10.1021/ja00242a034
• 作为产物：
  描述：

  5-苯基四氮唑 生成 phenylcarbene
  参考文献：
  名称：

  Kuzaj, Martin; Lueerssen, Holger; Wentrup, Curt, Angewandte Chemie, 1986, vol. 98, # 5, p. 476 - 477

  摘要：

  DOI：

文献信息

• Direct Observation of Carbene and Diazo Formation from Aryldiazirines by Ultrafast Infrared Spectroscopy
  作者：Yunlong Zhang、Gotard Burdzinski、Jacek Kubicki、Matthew S. Platz

  DOI：10.1021/ja805922b

  日期：2008.12.3

  first band is assigned to phenyldiazomethane, and the second is assigned to singlet phenylcarbene. This assignment is consistent with DFT calculations. Diazo band integration reveals that photoisomerization from diazirine to diazo occurs within a few picoseconds of the laser pulse. The majority of carbene produced is also formed instantaneously.

  苯基二氮嗪的超快激光闪光光解 (lambda(ex) = 270 nm) 在 2040 和 1582 cm(-1) 处产生瞬态红外吸收。第一个谱带归属于苯基重氮甲烷，第二个谱带归属于单线态苯基卡宾。此分配与 DFT 计算一致。重氮带积分表明从重氮到重氮的光异构化发生在激光脉冲的几皮秒内。产生的大部分卡宾也是瞬间形成的。
• Nitrile Imines: Matrix Isolation, IR Spectra, Structures, and Rearrangement to Carbodiimides
  作者：Didier Bégué、Greg GuangHua Qiao、Curt Wentrup

  DOI：10.1021/ja2118442

  日期：2012.3.21

  nitrile imines was investigated computationally at the B3LYP/6-31G* level. IR spectra were analyzed in terms of calculated anharmonic vibrational spectra and were generally in very good agreement with the calculated spectra. Infrared spectra were found to reflect the structures of nitrile imines accurately. Nitrile imines with IR absorptions above 2200 cm(-1) have essentially propargylic structures, possessing

  腈亚胺的结构和反应性是持续争论的主题。几种腈亚胺是通过光化学或热能产生的，并通过红外光谱在低温下在 Ar 基质中进行研究（Ph-CNN-H 6、Ph-CNN-CH(3)17、Ph-CNN-SiMe(3)23、Ph-CNN -Ph 29、Ph(3)C-CNN-CPh(3)34 和硼酸-CNN-硼酸衍生物 39)。在 B3LYP/6-31G* 水平计算研究了取代基对腈亚胺结构和红外吸收的影响。根据计算的非谐振动光谱分析红外光谱，并且通常与计算的光谱非常一致。发现红外光谱可以准确地反映腈亚胺的结构。红外吸收高于 2200 cm(-1) 的腈亚胺基本上具有炔丙基结构，具有 CN 三键（通常为 PhCNNSiMe(3)23、PhCNNPh 29 和硼酸-CNN-硼酸 39）。红外吸收低于约的腈亚胺。2200 cm(-1) 更可能是等离子（例如，HCNNH 1、PhCNNH 6、HCNNPh 43、PhCNNCH(3)17
• Cycloaddition of Bun3P·CS2: Direct one-pot conversion of strained double bonds to 2-alkylidene-1,3-dithiolanes
  作者：R. Alan Aitken、Katriona Carcas、Lawrence Hill、Tracy Massil、Swati V. Raut

  DOI：10.1016/s0040-4020(96)01128-3

  日期：1997.2

  adduct between tri-n-butylphosphine and carbon disulfide 1 with norbornene gives the novel zwitterionic structure 9. In solution this dissociates to the ylide 8 which undergoes Wittig reaction with aldehydes. Using the same method, the overall conversion of the strained double bond in a variety of bicyclo[2.2.1]alkenes into 2-benzylidene-1,3-dithioles 15–24 has been achieved and the reaction is also applicable

  三-之间的加合物的反应Ñ丁基膦和二硫化碳1与降冰片烯给出了新颖两性离子结构9。在溶液中，它解离为与醛进行Wittig反应的叶立德8。使用相同的方法，已将各种双环[2.2.1]烯烃中的应变双键整体转化为2-亚苄基-1,3-二硫醇15-24，该反应也适用于降冰片二烯，从而得到bis-dithiolanes 29-31。
• The disappearance of aryl carbenes in a reactive matrix
  作者：Cheng-Tung Lin、Peter P. Gaspar

  DOI：10.1016/0040-4039(80)80233-4

  日期：1980.1

  The disappearance of diphenylmethylene, fluorenylidene and phenylmethylene in isobutylene and fluorolube was monitored by esr spectroscopy at temperatures between 77°K and 171°K.

  通过电离能谱法在介于77°K和171°K之间的温度下监测异丁烯和氟润滑油中二苯基亚甲基，芴基和苯基亚甲基的消失。
• Evidence of Hydrogen Migration in an Alkylphenyldiazirine Excited State
  作者：Yunlong Zhang、Jacek Kubicki、Matthew S. Platz

  DOI：10.1021/ol101127c

  日期：2010.7.16

  Ultrafast photolysis (350 nm) of alkylphenyldiazirines promotes the diazirine to the Si excited state. Solvent and substituent effects on the excited state lifetimes indicate that the S-1 state is highly polarized and undergoes a [1,2]-H shift in concert with nitrogen extrusion in cyclohexane.