1-adamantyl tert-butyl ketoxime | 51643-26-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-adamantyl tert-butyl ketoxime
• 英文别名: 1-Adamantyl-tert.butylketoxim；N-[1-(1-adamantyl)-2,2-dimethylpropylidene]hydroxylamine
• CAS: 51643-26-6
• 化学式: C₁₅H₂₅NO
• 分子量: 235.37
• InChiKey: FDVSOSGOTXMNDR-UHFFFAOYSA-N

物化性质

• 沸点：
  349.8±9.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-adamantyl tert-butyl ketoxime 在 silver(l) oxide 作用下， 生成 1-Adamantyl-tert.butyliminoxyradikal
  参考文献：
  名称：

  Calorimetric and equilibrium studies on some stable nitroxide and iminoxy radicals. Approximate oxygen-hydrogen bond dissociation energies in hydroxylamines and oximes

  摘要：

  DOI：

  10.1021/ja00807a018
• 作为产物：
  描述：

  1-adamantyl tert-butyl ketone imine 在 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 为溶剂， 生成 1-adamantyl tert-butyl ketoxime
  参考文献：
  名称：

  Structural Effects on Stabilities of Iminoxy Radicals

  摘要：

  The equilibrium acidities for the O-H bonds of seven ketoximes in dimethyl sulfoxide and the oxidation potentials of their conjugate anions have been measured. The combination of the pK(HA) and E(OX)(A(-)) values using eq 1 has allowed estimates to be made of the ethalpies for homolytic cleavage of the O-H bonds (BDEs). The BDEs estimated for the O-H bonds in t-Bu(2)C=NOK-and t-Bu(1-Ad)C=NOH by our simple method using eq 1, BDE = 1.37pK(HA) + 23.1E(OX)(A(-)) + 73.3, were found to be within experimental error of those obtained by a direct calorimetric method. The BDEs of the O-H bonds become progressively weaker as the size of the alkyl groups R and R' in the RR'C=NOH oximes become larger. The BDEs cover a range of 14 kcal/mol from that of 95.8 kcal/mol for the BDE of the O-H bond in Me(2)C=NOH to 81.7 kcal/mol for the BDE of the O-H bond in t-Bu(Ad)C=NOH. The effects are rationalized in terms of increasing ground state energies and decreasing BDEs with increasing size of the alkyl groups, as the result of progressively larger relief of steric strain as the O-H bond is broken homolytically. These and other effects of structural changes in oximes on BDEs of their O-H bonds are consistent with delocalization of the odd electron in a p orbital on oxygen to carbon. The X-ray crystal structure of di-tert-butyl ketoxime has been measured and compared with that of dimethyl ketoxime.

  DOI：

  10.1021/ja00122a016

文献信息

• Calorimetric and equilibrium studies on some stable nitroxide and iminoxy radicals. Approximate oxygen-hydrogen bond dissociation energies in hydroxylamines and oximes
  作者：L. R. Mahoney、G. D. Mendenhall、K. U. Ingold

  DOI：10.1021/ja00807a018

  日期：1973.12
• Structural Effects on Stabilities of Iminoxy Radicals
  作者：F. G. Bordwell、Shizhong Zhang

  DOI：10.1021/ja00122a016

  日期：1995.5

  The equilibrium acidities for the O-H bonds of seven ketoximes in dimethyl sulfoxide and the oxidation potentials of their conjugate anions have been measured. The combination of the pK(HA) and E(OX)(A(-)) values using eq 1 has allowed estimates to be made of the ethalpies for homolytic cleavage of the O-H bonds (BDEs). The BDEs estimated for the O-H bonds in t-Bu(2)C=NOK-and t-Bu(1-Ad)C=NOH by our simple method using eq 1, BDE = 1.37pK(HA) + 23.1E(OX)(A(-)) + 73.3, were found to be within experimental error of those obtained by a direct calorimetric method. The BDEs of the O-H bonds become progressively weaker as the size of the alkyl groups R and R' in the RR'C=NOH oximes become larger. The BDEs cover a range of 14 kcal/mol from that of 95.8 kcal/mol for the BDE of the O-H bond in Me(2)C=NOH to 81.7 kcal/mol for the BDE of the O-H bond in t-Bu(Ad)C=NOH. The effects are rationalized in terms of increasing ground state energies and decreasing BDEs with increasing size of the alkyl groups, as the result of progressively larger relief of steric strain as the O-H bond is broken homolytically. These and other effects of structural changes in oximes on BDEs of their O-H bonds are consistent with delocalization of the odd electron in a p orbital on oxygen to carbon. The X-ray crystal structure of di-tert-butyl ketoxime has been measured and compared with that of dimethyl ketoxime.