2-acetoxy-4-benzoyl-1-oxa-4-azacyclohexane | 64918-12-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 2-acetoxy-4-benzoyl-1-oxa-4-azacyclohexane
• 英文别名: 2-acetoxy-4-benzoyl-morpholine；2-Acetoxy-4-benzoyl-1-oxa-4-azacyclohexan
• CAS: 64918-12-3
• 化学式: C₁₃H₁₅NO₄
• 分子量: 249.266
• InChiKey: BYZPSVHJJCJWSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.05
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-acetoxy-4-benzoyl-1-oxa-4-azacyclohexane 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 2.0h， 以66%的产率得到4-benzoyl-2,3-dihydro-4H-1,4-oxazine
  参考文献：
  名称：

  Effects of substitution on nitrogen on barriers to rotation of amides. 2—Evaluation of the importance of resonance effects

  摘要：

  AbstractAnalogs of N‐acetyl‐ and N‐benzoyl‐azacyclohex‐2‐enes having an oxygen atom, a methylene‐d2 group or a carbonyl group in place of the C‐4 methylene group have been synthesized. The amide rotational barriers in these compounds have been measured by the total line‐shape analysis of variable‐temperature 1H NMR spectra. The free energies of activation for both the N‐acetyl and N‐benzoyl series decrease in the sequence O≃CD2 > CO. The barriers for the first two compounds in each series are similar to those of the corresponding saturated analogs, a result which confirms recent reports that the long accepted barrier‐decreasing effect of an α‐olefinic substituent on nitrogen is counteracted. Evidence is presented that resonance stabilization of the rotational transition state in the unsaturated compounds still obtains. It is suggested that the introduction of an α‐olefinic substituent on nitrogen has a negligible effect on the amide rotational barriers in the cases of the oxygen and methylene‐d2 analogs, since any increase in the stabilization of the transition state by resonance is offset by the accompanying decrease in the sp3 character of the nitrogen atom. In cases in which a substituent on the olefinic group can interact directly with the lone pair on nitrogen, for example in the carbonyl analogs, then the resonance stabilization of the transition state is dominant.

  DOI：

  10.1002/mrc.1270221103
• 作为产物：
  描述：

  4-苯甲酰吗啉 、 过氧化乙酸叔丁酯 在 copper(l) chloride 作用下， 以 苯 为溶剂， 反应 5.5h， 生成 2-acetoxy-4-benzoyl-1-oxa-4-azacyclohexane
  参考文献：
  名称：

  Effects of substitution on nitrogen on barriers to rotation of amides. 2—Evaluation of the importance of resonance effects

  摘要：

  AbstractAnalogs of N‐acetyl‐ and N‐benzoyl‐azacyclohex‐2‐enes having an oxygen atom, a methylene‐d2 group or a carbonyl group in place of the C‐4 methylene group have been synthesized. The amide rotational barriers in these compounds have been measured by the total line‐shape analysis of variable‐temperature 1H NMR spectra. The free energies of activation for both the N‐acetyl and N‐benzoyl series decrease in the sequence O≃CD2 > CO. The barriers for the first two compounds in each series are similar to those of the corresponding saturated analogs, a result which confirms recent reports that the long accepted barrier‐decreasing effect of an α‐olefinic substituent on nitrogen is counteracted. Evidence is presented that resonance stabilization of the rotational transition state in the unsaturated compounds still obtains. It is suggested that the introduction of an α‐olefinic substituent on nitrogen has a negligible effect on the amide rotational barriers in the cases of the oxygen and methylene‐d2 analogs, since any increase in the stabilization of the transition state by resonance is offset by the accompanying decrease in the sp3 character of the nitrogen atom. In cases in which a substituent on the olefinic group can interact directly with the lone pair on nitrogen, for example in the carbonyl analogs, then the resonance stabilization of the transition state is dominant.

  DOI：

  10.1002/mrc.1270221103

文献信息

• Pinto,B.M. et al., Canadian Journal of Chemistry, 1977, vol. 55, p. 937 - 948
  作者：Pinto,B.M. et al.

  DOI：——

  日期：——