diphenylcarbene | 3129-17-7

• 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: diphenylcarbene
• 英文别名: Methylene, diphenyl-；cyclohexa-2,5-dien-1-ylidenemethylbenzene
• CAS: 3129-17-7
• 化学式: C₁₃H₁₀
• 分子量: 166.222
• InChiKey: XMGMFRIEKMMMSU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  diphenylcarbene 在 重水 作用下， 反应 17.0h， 生成 α,β-dideuteriobenzhydrol
  参考文献：
  名称：

  The Highly Reactive Benzhydryl Cation Isolated and Stabilized in Water Ice

  摘要：

  Diphenylcarbene (DPC) shows a triplet ground-state lying approximately 3 kcal/mol below the lowest singlet state. Under the conditions of matrix isolation at 25 K, DPC reacts with single water molecules embedded in solid argon and switches its ground state from triplet to singlet by forming a strong hydrogen bond. The complex between DPC and water is only metastable, and even at 3 K the carbene center slowly inserts into the OH bond of water to form benzhydryl alcohol via quantum chemical tunneling. Surprisingly, if DPC is generated in amorphous water ice at 3 K, it is protonated instantaneously to give the benzhydryl cation. Under these conditions, the benzhydryl cation is stable, and warming to temperatures above 50 K is required to produce benzhydryl alcohol. Thus, for the first time, a highly electrophilic and extremely reactive secondary carbenium ion can be isolated in a neutral, nucleophilic environment avoiding superacidic conditions.

  DOI：

  10.1021/ja507894x
• 作为产物：
  描述：

  二氯二苯甲烷 在 四甲基乙二胺 作用下， 以 甲基环己烷 为溶剂， 生成 diphenylcarbene
  参考文献：
  名称：

  An exceptionally simple method of preparing matrix-isolated biradicals, biradicaloids, and carbenes

  摘要：

  DOI：

  10.1021/ja00215a062

文献信息

• Carbocation formation via carbene protonation studied by the technique of stopped-flow laser-flash photolysis
  作者：Simon T. Belt、Cornelia Bohne、G. Charette、S. E. Sugamori、J. C. Scaiano

  DOI：10.1021/ja00059a014

  日期：1993.3

  Photolysis of diaryl diazo compounds in the presence of hydroxylic protonating substrates in acetonitrile leads to the formation of the corresponding carbocations. Quantum yields for these processes have been determined for the first time; for example, photolysis of diphenyldiazomethane in 1:1 acetonitrile/trifluoroethanol produces Ph 2 CH + with a quantum yield of 0.007. The products, formed either

  在乙腈中的羟基质子化底物存在下，二芳基重氮化合物的光解导致形成相应的碳正离子。首次确定了这些过程的量子产率；例如，二苯基重氮甲烷在 1:1 乙腈/三氟乙醇中的光解产生 Ph 2 CH + ，量子产率为 0.007。通过直接插入或通过碳正离子途径形成的产物是相应的醚。动力学分析得出的结论是碳正离子是由单线态卡宾的质子化形成的
• Reaction of diphenylcarbene with amines and the question of triplet-singlet equilibration
  作者：A. S. Nazran、David Griller

  DOI：10.1021/ja00302a002

  日期：1985.8

  Photolyse de l'α-diazo diphenylmethane conduisant au diphenylcarbene. Reaction de celui-ci avec la butylamine et la t-butylamine. Donnees cinetiques, mecanisme

  Photolyse de l'α-重氮二苯甲烷导管 au diphenylcarbene。反应 de celui-ci avec la 丁胺和叔丁胺。Donnees cinetiques, mecanisme
• Activation of the B−F Bond by Diphenylcarbene: A Reversible 1,2-Fluorine Migration between Boron and Carbon
  作者：Paolo Costa、Joel Mieres-Perez、Nesli Özkan、Wolfram Sander

  DOI：10.1002/anie.201610179

  日期：2017.2.6

  of BF3 in a two‐step reaction. The first step is the formation of a strongly bound Lewis acid–base complex between the singlet state of diphenylcarbene and BF3. This step involves an inversion of the spin state of the carbene from triplet to singlet. The second step requires visible‐light photochemical activation to induce a 1,2‐F migration from boron to the adjacent carbon atom under formation of the

  在低温基质中进行的实验表明，三重态二苯卡宾通过两步反应插入到BF 3的非常牢固的BF键中。第一步是在二苯卡宾的单线态和BF 3之间形成牢固结合的路易斯酸碱配合物。该步骤涉及将卡宾的自旋态从三重态转化为单重态。第二步需要可见光光化学活化，以在卡宾中心正式插入到BF 3的形成过程中诱导1,2-F从硼迁移到相邻的碳原子。1,2-F迁移在短波长紫外线照射下是可逆的，因此导致回到路易斯酸碱加合物。
• Laser flash spectrometric investigations of biradicals and caged radical pairs
  作者：Nicholas J. Turro

  DOI：10.1016/0040-4020(82)80161-0

  日期：1982.1

  The use of laser flash spectroscopic tecniques allows the detection, identification dynamic analysis of biradicals and caged pairs in fluid solution at ambient temperatures. The conventional flash spectroscopic device has been advanced with the advent of the Excimer Laser, as an excitation source of the optical multichannel analyzer (OMA) as a detector system and of the transient digitizer (TD) as

  激光闪光光谱技术的使用允许在环境温度下对流体溶液中的双自由基和笼对进行检测，鉴定动态分析。随着准分子激光器的出现，作为闪光灯的多通道分析仪（OMA）作为检测器系统，以及瞬态数字化仪（TD）作为数据收集器和分析仪的激发源，传统的闪光光谱仪得到了发展。准分子激光器除用作激发源外，还可能由于这种设备产生的异常高强度而引发新的光物理和/或光化学事件。
• Reaction of phenylchlorocarbene and diphenylcarbene with the carbon-chlorine bond: kinetics and mechanisms
  作者：Michelle B. Jones、Vincent M. Maloney、Matthew S. Platz

  DOI：10.1021/ja00032a034

  日期：1992.3

  The reactions of phenylchlorocarbene (PCC) and diphenylcarbene (DPC) with carbon-chlorine bonds were investigated by laser flash photolysis techniques, product studies, and electrochemical methods. The data with both carbenes are consistent with a polar chlorine atom transfer to form radical pairs. The PCC reaction can be thought of as an inner sphere electron transfer from the carbene to the carbon-halogen

  通过激光闪光光解技术、产物研究和电化学方法研究了苯基氯卡宾 (PCC) 和二苯基卡宾 (DPC) 与碳-氯键的反应。两种卡宾的数据与极性氯原子转移形成自由基对一致。PCC 反应可以被认为是从卡宾到碳卤键的内球电子转移，其中在过渡态中形成了部分碳卤键。过渡态被认为涉及闭壳和开壳单线态表面之间的交叉。DPC 与氯供体反应获得的数据类似于 PCC 获得的数据，但更难以解释，因为与 C-Cl 键反应的状态的多样性尚不清楚。40 个参考文献，10 个图，9 个标签。