acetone ketyl(d7) radical | 121003-93-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: acetone ketyl(d7) radical
• CAS: 121003-93-8
• 化学式: C₃H₇O
• 分子量: 66.0324
• InChiKey: YNWTXMOZDGPBDJ-UAVYNJCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.93
• 重原子数：
  4.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  氘代异丙醇 在 D 作用下， 以 高氯酸 、 重水 为溶剂， 生成 acetone ketyl(d7) radical
  参考文献：
  名称：

  Kinetic Isotope Effects in H and D Abstraction Reactions from Alcohols by D Atoms in Aqueous Solution

  摘要：

  Electron paramagnetic resonance free induction decay attenuation measurements were performed in the range of liquid D2O for the reactions of D atoms with undeuterated and deuterated alcohols. Excellent Arrhenius behavior represented by log(k/M-1 s(-1)) = (10.97 +/- 0.14) - [(24.7 +/- 0.8) kJ mol(-1)/2.303RT)] for CH3OD, log(k/M-1 s(-1)) = (11.09 +/- 0.12) - [(20.8 +/- 0.6) kJ mol(-1)/2.303RT)] for CH3CH2OD, log(k/M-1 s(-1)) = (11.45 +/- 0.10) - [(28.4 +/- 0.6) kJ mol(-1)/2.303RT)] for CD3CD2OD, log(k/M-1 s(-1)) = (11.32 +/- 0.15) - [(21.3 +/- 0.8) kJ mol(-1)/2.303RT)] for CH3CH2CH2OD, log(k/M-1 s(-1)) (11.60 +/- 0.06) - [(21.2 +/- 0.3) kJ mol(-1)/2.303RT)] for(CH3)(2)C(H)OD, log(k/M-1 s(-1)) = (11.48 +/- 0.12) - [(24.7 +/- 0.7) kJ mol(-1)/2.303RT)] for(CD3)(2)C(D)OD, was found in all cases. Compared with the gas phase, the reactions exhibit slightly higher activation energies, in agreement with expectation for solvation based on a predicted decrease of the dipole moment from the reactant alcohol to the transition state. A pronounced increase in Arrhenius preexponential factors is attributed mostly to equilibrium solvation of the D atom, but a significant difference between H2O and D2O suggests contributions of a dynamic solvent effect.

  DOI：

  10.1021/jp981936l

文献信息

• Using electron-transfer reactions to propagate radical chain processes
  作者：R. J. Kolt、D. D. M. Wayner、D. Griller

  DOI：10.1021/jo00278a059

  日期：1989.8
• Levstein, Patricia R.; Willigen, Hans van, Zeitschrift fur Physikalische Chemie, 1993, vol. 180, # 1/2, p. 33 - 50
  作者：Levstein, Patricia R.、Willigen, Hans van

  DOI：——

  日期：——
• Fourier transform‐electron paramagnetic resonance study of the photochemical reaction of acetone with 2‐propanol
  作者：Patricia R. Levstein、Hans van Willigen

  DOI：10.1063/1.461098

  日期：1991.7.15

  Fourier transform-electron paramagnetic resonance (FT-EPR) was used to study the pulsed-laser induced reduction of acetone with 2-propanol. By monitoring the EPR signal of the acetone ketyl radical as function of delay time (τd) between laser pulse and microwave pulse, with τd ranging from nanoseconds to 100 μs, information was obtained on the kinetics of free radical formation and decay. The time evolution of the signal also gave an insight into the chemically induced dynamic electron polarization (CIDEP) mechanisms that affect signal amplitudes. It was found that the spectra obtained with τd settings ranging from 0 to 400 ns contain a dispersive signal contribution that is due to the presence of spin-correlated radical pairs (SCRP) at the time of the microwave pulse. For acetone(D6) in 2-propanol(D8) the rate constants of formation and decay of the SCRP are found to be 7.5±3.7×106 and ∼5×107 s−1, respectively. The SCRP lifetime in 2-propanol(D8) at room temperature corresponds to what would be expected for diffusion controlled cage escape. The rate constant for ketyl(D7) radical formation is found to be 5.8±0.5×106 s−1. The decay rate constant kdN(0), where N(0) is the maximum radical concentration, is found to be 1.0×105 s−1. The rate constant for radical formation increases to 1.1×107 s−1 for the acetone(H6)/2-propanol(H8) system. The pronounced isotope effect on radical formation is consistent with a transition state involving C–H bond stretching. The FT-EPR spectra show the effects of radical pair CIDEP. However, a detailed analysis of signal growth and decay kinetics shows that there is no triplet mechanism CIDEP contribution. This finding is in agreement with the relative magnitudes of acetone triplet spin lattice relaxation and radical formation rate constants. The results also demonstrate that the rate constant for hydrogen abstraction is triplet sublevel independent.