(4,6-13C2)-2,2-dimethyl-1,3-dioxan-4,6-dione | 126395-75-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4,6-13C2)-2,2-dimethyl-1,3-dioxan-4,6-dione
• 英文别名: meldrum's acid<4,6-13C2>
• CAS: 126395-75-3
• 化学式: C₆H₈O₄
• 分子量: 146.105
• InChiKey: GXHFUVWIGNLZSC-MQIHXRCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.21
• 重原子数：
  10.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4,6-13C2)-2,2-dimethyl-1,3-dioxan-4,6-dione 以 乙醇 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Iminopropadienones, RN:C:C:C:O. Theory and experiment

  摘要：

  Ab initio molecular orbital calculations at the MP2/6-31G* level have been used to examine the structures and infrared spectra of a new class of compounds, the iminopropadienones, RN=C=C=C=O (R = H, CH3, and Ph). The agreement between calculated and experimental IR spectra of PhNCCCO, Ph(15)NCCCO, and PhNCC(13)CO is excellent. Inclusion of electron correlation is found to be important for the correct prediction of the relative intensities of the cumulenic stretching vibrations. All three iminopropadienones are predicted to have a slightly bent NCCCO backbone (angle CCC approximate to 176 degrees). As with carbon suboxide, these cumulenes are calculated to have an extremely flat CCC bending potential. The parent compound, HNCCCO (4a) is calculated to be thermodynamically stable toward dissociations into (i) HNCC + CO, (ii) HNC + CCO, (iii) HN + CCCO, and (iv) H. + NCCCO.. Rearrangement of 4a to the more stable cyanoketene isomer requires a sizeable barrier of 402 kJ mol(-1) [G2(MP2)]. The calculated stability of 4a is consistent with its experimental observation in neutralization-reionization mass spectrum. The adiabatic ionization energy and heat of formation of HNCCCO are predicted to be 9.51 eV and 175 kJ mol(-1), respectively.

  DOI：

  10.1021/j100055a007
• 作为产物：
  描述：

  丙二酸-1,3-13C2 生成 (4,6-13C2)-2,2-dimethyl-1,3-dioxan-4,6-dione
  参考文献：
  名称：

  Iminopropadienones, RN:C:C:C:O. Theory and experiment

  摘要：

  Ab initio molecular orbital calculations at the MP2/6-31G* level have been used to examine the structures and infrared spectra of a new class of compounds, the iminopropadienones, RN=C=C=C=O (R = H, CH3, and Ph). The agreement between calculated and experimental IR spectra of PhNCCCO, Ph(15)NCCCO, and PhNCC(13)CO is excellent. Inclusion of electron correlation is found to be important for the correct prediction of the relative intensities of the cumulenic stretching vibrations. All three iminopropadienones are predicted to have a slightly bent NCCCO backbone (angle CCC approximate to 176 degrees). As with carbon suboxide, these cumulenes are calculated to have an extremely flat CCC bending potential. The parent compound, HNCCCO (4a) is calculated to be thermodynamically stable toward dissociations into (i) HNCC + CO, (ii) HNC + CCO, (iii) HN + CCCO, and (iv) H. + NCCCO.. Rearrangement of 4a to the more stable cyanoketene isomer requires a sizeable barrier of 402 kJ mol(-1) [G2(MP2)]. The calculated stability of 4a is consistent with its experimental observation in neutralization-reionization mass spectrum. The adiabatic ionization energy and heat of formation of HNCCCO are predicted to be 9.51 eV and 175 kJ mol(-1), respectively.

  DOI：

  10.1021/j100055a007

文献信息

• Brown, Roger F. C.; Browne, Neil R.; Coulston, Karen J., Australian Journal of Chemistry, 1989, vol. 42, # 8, p. 1321 - 1344
  作者：Brown, Roger F. C.、Browne, Neil R.、Coulston, Karen J.、Eastwood, Frank W.、Irvine, Margaret J.、et al.

  DOI：——

  日期：——