1-isocyano-2-(N-acetylamino)-ethane | 137465-87-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-isocyano-2-(N-acetylamino)-ethane
• 英文别名: 1-isocyano-2-(acetylamino)ethane；N-(2-isocyanoethyl)acetamide
• CAS: 137465-87-3
• 化学式: C₅H₈N₂O
• 分子量: 112.131
• InChiKey: IISJYGPAUQOTKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  33.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5,6-二甲基-2,3-二氢吡嗪 在 氧气 、 rose bengal 作用下， 以 乙腈 为溶剂， 反应 13.0h， 以55%的产率得到1-isocyano-2-(N-acetylamino)-ethane
  参考文献：
  名称：

  2,3-二氢吡嗪的光敏氧化：异腈的意外合成

  摘要：

  5，6-二甲基-（1a）和5-甲基-6-苯基-2，3-二氢吡嗪（1b）的玫瑰孟加拉和四苯基卟啉敏化的光氧合反应生成1-异氰基-2-（N-乙酰氨基）-乙烷（2a）和1-异氰基-2-（N-苯甲酰基氨基）-乙烷（2b）。5，6-二苯基-2，3-二氢吡嗪（1c）在反应条件下是惰性的。

  DOI：

  10.1016/s0040-4039(00)86667-8

文献信息

• Solvent effect on the sensitized photooxygenation of cyclic and acyclic α-diimines
  作者：Else Lemp、Antonio L. Zanocco、German Günther、Nancy Pizarro

  DOI：10.1016/j.tet.2006.08.091

  日期：2006.11

  The reaction of singlet molecular oxygen with a series of cyclic and acyclic α-diimines was studied. Time-resolved methods were used to measure total reaction rate constants and steady-state methods were used to determine chemical reaction rate constants. GC–MS was used to tentatively assign the reaction products. 5,6-Disubstituted cyclic α-diimines are singlet oxygen quenchers, but become more effective

  研究了单线态分子氧与一系列环状和非环状α-二亚胺的反应。时间分辨方法用于测量总反应速率常数，稳态方法用于确定化学反应速率常数。用GC-MS暂定反应产物。5,6-二取代的环状α-二亚胺是单线态氧猝灭剂，但在极性溶剂中变得更有效。涉及过氧化物中间体或过渡态导致氢过氧化物的反应机理似乎是产物形成的关键反应路径。用苯基取代基取代甲基取代基会引发另一种反应，该反应涉及过氧化物样的激基复合物，从而增加了环状α-二亚胺的单线态氧猝灭。5的反应性 朝向单线态氧的6-二取代环状α-二亚胺高度依赖于邻位苯环和电子效应引起的空间相互作用。相比之下，1，4-二取代的无环α-二亚胺是中等或较差的单线态氧猝灭剂。总速率常数几乎不取决于溶剂性质，而是与Hildebrand参数相关。这些结果是根据涉及二氧杂环丁烷样激基复合物的机理来解释的，该机理产生带电荷的中间体，从而导致产物。而是与Hildebrand参数相关联。这些
• Photooxygenation of 1,4-diaza-1,3-butadienes (.alpha.-diimines): formation of isonitriles
  作者：Klaus Gollnick、Sigrid Koegler、Dorothee Maurer

  DOI：10.1021/jo00027a041

  日期：1992.1

  Dye-sensitized photooxygenations of cyclic and acyclic 1,4-diaza-1,3-butadienes (alpha-diimines), carrying a methyl or an ethyl group in the 2-position, yield isonitriles and amides, as well as formaldehyde or acetaldehyde. Thus, cyclic alpha-diimines such as 5,6-dimethyl- (1a), 5-methyl-6-phenyl- (1b), 5-methyl-6-(p-tolyl)- (1c), and 5,6-diethyl-2,3-dihydropyrazine (1d) yield the respective 1-isocyano-2-(acylamino)ethanes 2a-d, whereas 5-isopropyl-6-phenyl- (1e) and 5,6-diphenyl-2,3-dihydropyrazine (1f) are inert toward photooxygenation. Acyclic alpha-diimines such as 1,8-bis(acetylamino)-3,6-diaza-4,5-dimethyl-3,5-octadiene (4a), 2,5-diaza-3,4-dimethyl-2,4-hexadiene (4b), 1,4-diaza-2,3-dimethyl-1,4-diphenyl-1,3-butadiene (4c), and N,N'-bis[(1S,2S,3S,5R)-pinan-3-ylmethyl]-2,3-butanediimine (4d) afford the respective isonitriles 5a-d and acetamides 6a-d. With retention of configuration, chiral alpha-diimines such as (-)-N,N'-bis[(S)-1-phenylethyl]-2,3-butanediimine [(S,S)-4e] and its R,R enantiomer [(R,R,)-4e], and (3S,8S)-(-)-3,8-dicarbomethoxy-4,7-diaza-2,5,6,9-tetramethyl-4,6-decadiene [(S,S)-4f] yield the corresponding enantiomerically pure isonitriles (S)-5e, (R)-5e, and (S)-5f and acetamides (S)-6e, (R)-6e, and (S)-6f. Evidence for a singlet oxygen reaction is presented. A working hypothesis is proposed which includes the formation of a transient hydroperoxide 7 that fragments into an isonitrile molecule, an aldehyde, and an N-alkyl- or N-arylnitrilium cation and a hydroxide ion; the latter combine to yield the amide groups in 2a-d and the amide compounds 6a-f.
• Photosensitized oxygenation of 2,3-dihydropyrazines: Unexpected synthesis of isonitriles
  作者：Klaus Gollnick、Sigrid Koegler

  DOI：10.1016/s0040-4039(00)86667-8

  日期：1988.1

  Rose bengal and tetraphenylporphin sensitized photooxygenations of 5, 6-dimethyl- (1a) and 5-methyl-6-phenyl-2, 3-dihydropyrazine (1b) yield 1-isocyano-2-(N-acetylamino)-ethane (2a) and 1-isocyano-2-(N-benzoylamino)-ethane (2b), respectively. 5,6-Diphenyl-2,3-dihydropyrazine (1c) is inert under the reaction conditions.

  5，6-二甲基-（1a）和5-甲基-6-苯基-2，3-二氢吡嗪（1b）的玫瑰孟加拉和四苯基卟啉敏化的光氧合反应生成1-异氰基-2-（N-乙酰氨基）-乙烷（2a）和1-异氰基-2-（N-苯甲酰基氨基）-乙烷（2b）。5，6-二苯基-2，3-二氢吡嗪（1c）在反应条件下是惰性的。