2-(4-cyano-phenyl)-2-oxo-ethyl | 69039-63-0

• 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: 2-(4-cyano-phenyl)-2-oxo-ethyl
• CAS: 69039-63-0
• 化学式: C₉H₆NO
• 分子量: 144.153
• InChiKey: ACLFNKZEQVOOTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.58
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  40.86
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  2-溴-4'-氰基苯乙酮 在 tetrabutylammonium tetrafluoroborate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-(4-cyano-phenyl)-2-oxo-ethyl
  参考文献：
  名称：

  协调和逐步解离电子转移。离去基团的氧化性和断裂键的强度作为α-取代苯乙酮的电化学还原说明的机制和反应性控制因素

  摘要：

  对一系列 α-取代苯乙酮的循环伏安研究允许鉴定解离电子转移反应的协调和逐步特征，并且在逐步情况下，确定裂解速率常数和标准电位形成阴离子自由基。使用源自实验和文献的热力学参数分析数据指向三个机制控制因素，离去基团的氧化性、键断裂的键解离能和LUMO能量。在许多情况下，这些因素中的第一个似乎在控制协调与逐步二分法方面占主导地位。氟取代基提供了一个相反的例子，其中键强度克服了离去基团氧化性的不利影响。就阴离子自由基裂解反应性而言，这也是一个例外，其中 C-F 键的强度显着有助于减缓...

  DOI：

  10.1021/ja963674b

文献信息

• Electrochemistry of Electron Transfer Probes. Observation of the Transition from Activation to Counterdiffusion Control in the Fragmentation of α-Aryloxyacetophenone Radical Anions¹^a
  作者：Mogens L. Andersen、William Long、Danial D. M. Wayner

  DOI：10.1021/ja963374u

  日期：1997.7.1

  The cleavage of radical anions of substituted alpha-phenoxyacetophenones, X-C6H4COCH2OPh, IIa-k, has been studied in DMF by voltammetric and coulometric techniques. The standard potentials (E degrees) for formation of and rate constants, k, for the cleavage of the radical anions were determined using linear sweep voltammetry, LSV, together with digital simulation and previously reported laser flash photolysis data. The rate constants cover a range of almost eight orders of magnitude (0.4 s(-1) for X = p-MeCO- to 1.3.10(7) s(-1) for X = p-MeO-). The relative driving forces, Delta Delta G degrees(het)(RX.-), for the heterolytic cleavage of the radical anions (to give R-. + X-) were estimated from thermochemical cycles. A combined plot of log(k) versus Delta Delta G(het)degrees(RX.-) for the radical anions of IIa-k and of alpha-aryloxyacetophenones gave a curve with alpha = 0.5 at high driving forces and alpha = 1 at low driving forces, where alpha = partial derivative Delta G(0)(double dagger)/partial derivative Delta G degrees. The plot was analyzed using a model in which reversible cleavage of the radical anions takes place inside the solvent cage followed by (counter)diffusion of the fragments out of the solvent cage. The change in the value of a is interpreted as a change in the rate limiting process from chemical activation (i.e.,, fragmentation) to counterdiffusion. The model allowed the determination of the absolute values of Delta G(het)degrees(RX.-) and the intrinsic barrier, Delta G(0)(double dagger), for the fragmentation of the radical anions (8 +/- 1 kcal mol(-1), 0.35 eV). This leads to an estimate of the homolytic bond dissociation free energy of the C-OPh bond in the unsubstituted alpha-phenoxyacetophenone.
• Solvent Reorganization as a Governing Factor in the Kinetics of Intramolecular Dissociative Electron Transfers. Cleavage of Anion Radicals of α-Substituted Acetophenones
  作者：Claude P. Andrieux、Jean-Michel Savéant、André Tallec、Robert Tardivel、Caroline Tardy

  DOI：10.1021/ja9622564

  日期：1996.1.1