2-(N-(Cyanomethyl)-N-methylamino)ethyl diazoacetate | 159050-52-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-(N-(Cyanomethyl)-N-methylamino)ethyl diazoacetate
• 英文别名: 2-[Cyanomethyl(methyl)amino]ethyl 2-diazoacetate；2-[cyanomethyl(methyl)amino]ethyl 2-diazoacetate
• CAS: 159050-52-9
• 化学式: C₇H₁₀N₄O₂
• 分子量: 182.182
• InChiKey: BHXRDIKEWUXIDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  55.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(N-(Cyanomethyl)-N-methylamino)ethyl diazoacetate 在 copper acetylacetonate 作用下， 以 甲苯 为溶剂， 反应 1.33h， 以19%的产率得到(4-甲基-2-氧代-3-吗啉基)乙腈
  参考文献：
  名称：

  Applications of Stevens [1,2]-Shifts of Cyclic Ammonium Ylides. A Route to Morpholin-2-ones

  摘要：

  2-(N,N-Dialkylamino)ethyl diazoacetoacetates 2 were prepared in two steps from readily available ethanolamines 1. When heated in the presence of catalytic Cu, the substrates cleanly formed morpholinones 3, presumably via the intermediacy of copper carbenoids and cyclic ammonium ylides. In most cases involving benzylic or allylic migrating groups, ylide [1,2]-shift occurred in good yield (55-80%). In the case of benzhydryl containing substrate 2g, only dimer 4 was isolated. Simple alkyl groups failed to undergo the rearrangement, with the exception of tert-butyl case 2i, which furnished morpholinone 3i in low yield. Substituted allylic case 2l gave only [1,2]-shift product 3l, with no evidence for competing [2,3]-shift to give 3l'. Diazoacetates 2n-p also underwent conversion to morpholinones 3n-p in 19-64% yield with Cu(acac)(2) catalysis.

  DOI：

  10.1021/jo00099a041
• 作为产物：
  描述：

  2-Cyanomethyl(2-hydroxyethyl)methylamine 在 四氢吡咯 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 二氯甲烷 为溶剂， 反应 40.0h， 生成 2-(N-(Cyanomethyl)-N-methylamino)ethyl diazoacetate
  参考文献：
  名称：

  Applications of Stevens [1,2]-Shifts of Cyclic Ammonium Ylides. A Route to Morpholin-2-ones

  摘要：

  2-(N,N-Dialkylamino)ethyl diazoacetoacetates 2 were prepared in two steps from readily available ethanolamines 1. When heated in the presence of catalytic Cu, the substrates cleanly formed morpholinones 3, presumably via the intermediacy of copper carbenoids and cyclic ammonium ylides. In most cases involving benzylic or allylic migrating groups, ylide [1,2]-shift occurred in good yield (55-80%). In the case of benzhydryl containing substrate 2g, only dimer 4 was isolated. Simple alkyl groups failed to undergo the rearrangement, with the exception of tert-butyl case 2i, which furnished morpholinone 3i in low yield. Substituted allylic case 2l gave only [1,2]-shift product 3l, with no evidence for competing [2,3]-shift to give 3l'. Diazoacetates 2n-p also underwent conversion to morpholinones 3n-p in 19-64% yield with Cu(acac)(2) catalysis.

  DOI：

  10.1021/jo00099a041

文献信息

• West F. G., Naidu B. N., J. Org. Chem, 59 (1994) N 20, S 6051-6056
  作者：West F. G., Naidu B. N.

  DOI：——

  日期：——
• Applications of Stevens [1,2]-Shifts of Cyclic Ammonium Ylides. A Route to Morpholin-2-ones
  作者：F. G. West、B. N. Naidu

  DOI：10.1021/jo00099a041

  日期：1994.10

  2-(N,N-Dialkylamino)ethyl diazoacetoacetates 2 were prepared in two steps from readily available ethanolamines 1. When heated in the presence of catalytic Cu, the substrates cleanly formed morpholinones 3, presumably via the intermediacy of copper carbenoids and cyclic ammonium ylides. In most cases involving benzylic or allylic migrating groups, ylide [1,2]-shift occurred in good yield (55-80%). In the case of benzhydryl containing substrate 2g, only dimer 4 was isolated. Simple alkyl groups failed to undergo the rearrangement, with the exception of tert-butyl case 2i, which furnished morpholinone 3i in low yield. Substituted allylic case 2l gave only [1,2]-shift product 3l, with no evidence for competing [2,3]-shift to give 3l'. Diazoacetates 2n-p also underwent conversion to morpholinones 3n-p in 19-64% yield with Cu(acac)(2) catalysis.