3-(Phenoxyacetyl)benzonitrile | 166190-02-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(Phenoxyacetyl)benzonitrile
• 英文别名: 3-(2-phenoxyacetyl)benzonitrile
• CAS: 166190-02-9
• 化学式: C₁₅H₁₁NO₂
• 分子量: 237.258
• InChiKey: RDYVYYWWEJFVEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(Phenoxyacetyl)benzonitrile 在 反-4,4'-二甲氧基芪 、 四丁基醋酸铵 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  不稳定芳基酮的自由基阴离子的光化学生成

  摘要：

  The radical anions of a series of substituted alpha-(aryloxy)acetophenones have been generated by trapping the solvated electron produced by 355-nm laser-induced photoionization of 4,4'-dimethoxystilbene in either acetonitrile or dimethylformamide (DMF). The radical anion of the parent ketone, alpha-phenoxyacetophenone, has lambda(max) at 500 nm and decays with a rate constant 7 x 10(5) s(-1). This rate constant reflects the rate of beta-cleavage to generate phenoxide ion and phenacyl radical. The rate constant for beta-cleavage decreases for ketones with electron donating substituents in the alpha-aryloxy ring. Substituent effects on the aceotphenone ring are in the opposite direction, and many of the 4-substituted (aryloxy)acetophenones have half-lives in excess of 10 mu s that reflect a combination of second order processes and are not limited by beta-cleavage. The generality of the photoionization/electron trapping method for the generation of radical anions of ketones with short-lived excited states that preclude direct excitation is illustrated by its application to other aryl ketones that undergo alpha-cleavage, beta-phenyl quenching, and intramolecular hydrogen abstraction reactions.

  DOI：

  10.1021/j100020a048
• 作为产物：
  描述：

  3-(2-溴乙酰基)苯甲腈 、 苯酚 在 potassium carbonate 作用下， 生成 3-(Phenoxyacetyl)benzonitrile
  参考文献：
  名称：

  不稳定芳基酮的自由基阴离子的光化学生成

  摘要：

  The radical anions of a series of substituted alpha-(aryloxy)acetophenones have been generated by trapping the solvated electron produced by 355-nm laser-induced photoionization of 4,4'-dimethoxystilbene in either acetonitrile or dimethylformamide (DMF). The radical anion of the parent ketone, alpha-phenoxyacetophenone, has lambda(max) at 500 nm and decays with a rate constant 7 x 10(5) s(-1). This rate constant reflects the rate of beta-cleavage to generate phenoxide ion and phenacyl radical. The rate constant for beta-cleavage decreases for ketones with electron donating substituents in the alpha-aryloxy ring. Substituent effects on the aceotphenone ring are in the opposite direction, and many of the 4-substituted (aryloxy)acetophenones have half-lives in excess of 10 mu s that reflect a combination of second order processes and are not limited by beta-cleavage. The generality of the photoionization/electron trapping method for the generation of radical anions of ketones with short-lived excited states that preclude direct excitation is illustrated by its application to other aryl ketones that undergo alpha-cleavage, beta-phenyl quenching, and intramolecular hydrogen abstraction reactions.

  DOI：

  10.1021/j100020a048

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.
• Photochemical Generation of Radical Anions of Photolabile Aryl Ketones
  作者：N. Mathivanan、L. J. Johnston、D. D. M. Wayner

  DOI：10.1021/j100020a048

  日期：1995.5

  The radical anions of a series of substituted alpha-(aryloxy)acetophenones have been generated by trapping the solvated electron produced by 355-nm laser-induced photoionization of 4,4'-dimethoxystilbene in either acetonitrile or dimethylformamide (DMF). The radical anion of the parent ketone, alpha-phenoxyacetophenone, has lambda(max) at 500 nm and decays with a rate constant 7 x 10(5) s(-1). This rate constant reflects the rate of beta-cleavage to generate phenoxide ion and phenacyl radical. The rate constant for beta-cleavage decreases for ketones with electron donating substituents in the alpha-aryloxy ring. Substituent effects on the aceotphenone ring are in the opposite direction, and many of the 4-substituted (aryloxy)acetophenones have half-lives in excess of 10 mu s that reflect a combination of second order processes and are not limited by beta-cleavage. The generality of the photoionization/electron trapping method for the generation of radical anions of ketones with short-lived excited states that preclude direct excitation is illustrated by its application to other aryl ketones that undergo alpha-cleavage, beta-phenyl quenching, and intramolecular hydrogen abstraction reactions.