1-acetyl-1-methyl-2-oxo-propyl | 17443-20-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-acetyl-1-methyl-2-oxo-propyl
• CAS: 17443-20-8
• 化学式: C₆H₉O₂
• 分子量: 113.136
• InChiKey: VXUYYDKQTYSIIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-甲基-2,4-戊烷二酮 在 二叔丁基过氧化物 、 trimethylamine borane 作用下， 以 氯苯 为溶剂， 生成 1-acetyl-1-methyl-2-oxo-propyl
  参考文献：
  名称：

  Estimation of Bond Dissociation Energies and Radical Stabilization Energies by ESR Spectroscopy

  摘要：

  Correlations of various indices of the stability and reactivity of carbon-centered radicals with ESR hyperfine splitting constants have been examined. For a large number of mono-and disubstituted radicals there is a moderately good linear correlation of alpha-proton hyperfine splitting constants (a(H-alpha) with radical stabilization enthalpies (RSE) and with BDE(C-H), the C-H bond-dissociation energies for the corresponding parent compounds determined from thermodynamic and kinetic studies of C-C homolysis reactions. There is a similarly satisfactory linear correlation of a(H-alpha) with BDE(C-H) determined by Bordwell's electrochemical and acidity function method. In all cases the correlations fail for nonplanar radicals. As expected, beta-proton hyperfine splitting constants (a(HbetaMe)) for radicals with a freely rotating methyl substituent are less sensitive to deviations from planarity and give better linear correlations with RSE and BDE(C-H). The correlations cover a range of more than 20 kcal/mol and are reliable predictors of RSE and BDE(C-H) for a variety of radicals including captodative species. However, the correlations fail for significantly nonplanar radicals and for radicals with cyclic delocalized systems, e.g., cyclopentadienyl. The ratio a(HbetaMe)/a(H-alpha for suitably substituted radicals provides an index of pyramidalization and allows one to decide for which compounds values of RSE and BDE(C-H) can be confidently estimated.

  DOI：

  10.1021/jo971940d

文献信息

• Establishment of the C−NO Bond Dissociation Energy Scale in Solution and Its Application in Analyzing the Trend of NO Transfer from <i>C</i>-Nitroso Compound to Thiols
  作者：Xin Li、Hui Deng、Xiao-Qing Zhu、Xiaoxiao Wang、Hao Liang、Jin-Pei Cheng

  DOI：10.1021/jo900732b

  日期：2009.6.19

  The first set of experimentally determined C−NO bond homolytic and heterolytic dissociation enthalpies in solution is derived by using direct titration calorimetry combined with appropriate electrode potentials through thermodynamic cycles. The homolytic bond dissociation energy scale (BDEs) of the corresponding C−NO bonds in the gas phase was also calculated at the MP2/6-311+G**//B3LYP/6-31G* level

  通过使用直接滴定热法结合适当的电势通过热力学循环，得出溶液中第一组实验确定的C-NO键的均质和异质解离焓。在MP2 / 6-311 + G ** // B3LYP / 6-31G *和BP86 / 6-31G *的水平下，还计算了气相中相应C-NO键的均相键解离能级（BDE）。 // B3LYP / 6-31G *出于比较目的的理论水平。使用C-NO和S-NO键的热力学参数来预测NO在乙腈溶液中从C-亚硝基底物转移到硫醇的趋势。
• Estimation of Bond Dissociation Energies and Radical Stabilization Energies by ESR Spectroscopy
  作者：Jochen J. Brocks、Hans-Dieter Beckhaus、Athelstan L. J. Beckwith、Christoph Rüchardt

  DOI：10.1021/jo971940d

  日期：1998.3.1

  Correlations of various indices of the stability and reactivity of carbon-centered radicals with ESR hyperfine splitting constants have been examined. For a large number of mono-and disubstituted radicals there is a moderately good linear correlation of alpha-proton hyperfine splitting constants (a(H-alpha) with radical stabilization enthalpies (RSE) and with BDE(C-H), the C-H bond-dissociation energies for the corresponding parent compounds determined from thermodynamic and kinetic studies of C-C homolysis reactions. There is a similarly satisfactory linear correlation of a(H-alpha) with BDE(C-H) determined by Bordwell's electrochemical and acidity function method. In all cases the correlations fail for nonplanar radicals. As expected, beta-proton hyperfine splitting constants (a(HbetaMe)) for radicals with a freely rotating methyl substituent are less sensitive to deviations from planarity and give better linear correlations with RSE and BDE(C-H). The correlations cover a range of more than 20 kcal/mol and are reliable predictors of RSE and BDE(C-H) for a variety of radicals including captodative species. However, the correlations fail for significantly nonplanar radicals and for radicals with cyclic delocalized systems, e.g., cyclopentadienyl. The ratio a(HbetaMe)/a(H-alpha for suitably substituted radicals provides an index of pyramidalization and allows one to decide for which compounds values of RSE and BDE(C-H) can be confidently estimated.