β-formyl-β-nitroenamine | 181294-57-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: β-formyl-β-nitroenamine
• 英文别名: 4-aza-2-nitro-2-heptenal；2-Nitro-3-(propylamino)prop-2-enal；2-nitro-3-(propylamino)prop-2-enal
• CAS: 181294-57-5
• 化学式: C₆H₁₀N₂O₃
• 分子量: 158.157
• InChiKey: JZWHLYUSJXNAGG-UHFFFAOYSA-N

物化性质

• 沸点：
  374.3±32.0 °C(Predicted)
• 密度：
  1.130±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  74.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  β-formyl-β-nitroenamine 在 盐酸羟胺 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以33%的产率得到4-硝基异恶唑
  参考文献：
  名称：

  New Synthetic Equivalent of Nitromalonaldehyde Treatable in Organic Media

  摘要：

  beta-Nitroenamines having a formyl group at the beta-position behave as the synthetic equivalent of unstable nitromalonaldehyde, which is a useful synthon for syntheses of versatile nitro compounds. High solubility of the nitroenamines into general organic solvents enables us to conduct reactions in the organic media accompanied by easy experimental manipulations and considerable safety. When nitroenamines are treated with 1,2-bifunctional nucleophiles such as hydrazines, hydroxylamine and glycine ester, nitrated pyrazoles, isoxazole and pyrrole-2-carboxylate were readily prepared. This methodology was also applicable to guanidines and 1,2-diamines, leading to pyrimidines and 1,4-diazepines, respectively.

  DOI：

  10.1021/jo0488513
• 作为产物：
  描述：

  {(E)-2-Nitro-3-[(Z)-propylimino]-propenyl}-propyl-amine 在 silica gel 作用下， 反应 24.0h， 以93%的产率得到β-formyl-β-nitroenamine
  参考文献：
  名称：

  New Synthetic Equivalent of Nitromalonaldehyde Treatable in Organic Media

  摘要：

  beta-Nitroenamines having a formyl group at the beta-position behave as the synthetic equivalent of unstable nitromalonaldehyde, which is a useful synthon for syntheses of versatile nitro compounds. High solubility of the nitroenamines into general organic solvents enables us to conduct reactions in the organic media accompanied by easy experimental manipulations and considerable safety. When nitroenamines are treated with 1,2-bifunctional nucleophiles such as hydrazines, hydroxylamine and glycine ester, nitrated pyrazoles, isoxazole and pyrrole-2-carboxylate were readily prepared. This methodology was also applicable to guanidines and 1,2-diamines, leading to pyrimidines and 1,4-diazepines, respectively.

  DOI：

  10.1021/jo0488513

文献信息

• Formylnitroenamines: useful building blocks for nitrated pyridones and aminopyridines with functional groups
  作者：Yumi Nakaike、Daisuke Hayashi、Nagatoshi Nishiwaki、Yoshito Tobe、Masahiro Ariga

  DOI：10.1039/b815306j

  日期：——

  therefore, serve as C3N1 building blocks having a nitro group to afford nitropyridones and aminonitropyridines with a functional group at the 3-position. Upon treatment with malonic acid derivatives or β-keto esters, nitropyridones were obtained, whereas reactions with functionalized acetonitriles afford aminonitropyridines, via a formal transfer of an alkyl group from the ring nitrogen to the imino group

  β-甲酰基-β-亚硝胺1同时具有亲电甲酰基和亲核氨基，因此，作为具有硝基的C 3 N 1结构单元，可以提供在3-位具有官能团的硝基吡啶酮和氨基硝基吡啶。经治疗丙二酸可以得到硝基吡啶酮衍生物或β-酮酯，而与官能化乙腈的反应则是通过烷基从环氮到亚氨基的正式转移而得到氨基硝基吡啶。这些程序提供了制备具有硝基的杂环的实用方法。
• Facile Synthesis of Functionalized Nitroenamines. III. Aminolysis of 1-Methyl-5-nitropyrimidin-2(1<i>H</i>)-one
  作者：Nagatoshi Nishiwaki、Yasuo Tohda、Masahiro Ariga

  DOI：10.1246/bcsj.69.1997

  日期：1996.7

  The aminolysis of 1-methyl-5-nitropyrimidin-2(1H)-one furnished diimines of nitromalonaldehyde in good yields. One of the imino groups of the diimines was readily hydrolyzed on silica gel to give nitroenamines possessing a formyl group. These reagents behaved as the synthetic equivalent of unstable nitromalonaldehyde, affording azaheterocycles upon a treatment with hydrazines or diamines.

  1-甲基-5-硝基吡啶-2(1H)-酮的氨解反应生成了较高产率的硝基丙二醛二亚胺。其中一个亚胺基团在硅胶上易于水解，得到具有甲酰基的硝基胺。这些试剂表现出不稳定硝基丙二醛的合成等效性，与肼或二胺反应时形成了氮杂杂环。
• Construction of 3,5-dinitrated 1,4-dihydropyridines modifiable at 1,4-positions by a reaction of β-formyl-β-nitroenamines with aldehydes
  作者：Haruyasu Asahara、Mai Hamada、Yumi Nakaike、Nagatoshi Nishiwaki

  DOI：10.1039/c5ra19439c

  日期：——

  A novel and efficient method for the synthesis of 4-substituted 3,5-dinitro-1,4-dihydropyridines by a reaction of β-formyl-β-nitroenamines with aldehydes was developed.

  开发了一种新颖高效的方法，通过β-甲醛基-β-硝基烯胺与醛反应合成4-取代的3,5-二硝基-1,4-二氢吡啶。
• Synthesis and intramolecular ring transformation of <i>N</i>,<i>N</i>′-dialkylated 2,6,9-triazabicyclo[3.3.1]nonadienes
  作者：Yumi Nakaike、Yusuke Yoshida、Soichi Yokoyama、Akitaka Ito、Nagatoshi Nishiwaki

  DOI：10.1039/d0ob01950j

  日期：——

  first and facile synthesis of N,N′-dialkylated 2,6,9-triazabicyclo[3.3.1]nonadienes was achieved by the [4 + 4] self-condensation of β-formyl-β-nitroenamine in the presence of ammonium acetate. The 2,6- and 2,9-dialkylated products were found to be interconvertible when dissolved in a solvent. This isomerization proceeds through intramolecular ring transformation via a common intermediate under equilibrium

  N , N'-二烷基化 2,6,9-三氮杂双环[3.3.1]壬二烯的首次且简便的合成是通过 β-甲酰基-β-硝基烯胺在铵存在下的 [4 + 4] 自缩合实现的醋酸盐。发现 2,6-和 2,9-二烷基化产物溶解在溶剂中时可相互转化。这种异构化通过平衡下的共同中间体通过分子内环转化进行。
• New Synthetic Equivalent of Nitromalonaldehyde Treatable in Organic Media
  作者：Nagatoshi Nishiwaki、Takuma Ogihara、Toshiko Takami、Mina Tamura、Masahiro Ariga

  DOI：10.1021/jo0488513

  日期：2004.11.1

  beta-Nitroenamines having a formyl group at the beta-position behave as the synthetic equivalent of unstable nitromalonaldehyde, which is a useful synthon for syntheses of versatile nitro compounds. High solubility of the nitroenamines into general organic solvents enables us to conduct reactions in the organic media accompanied by easy experimental manipulations and considerable safety. When nitroenamines are treated with 1,2-bifunctional nucleophiles such as hydrazines, hydroxylamine and glycine ester, nitrated pyrazoles, isoxazole and pyrrole-2-carboxylate were readily prepared. This methodology was also applicable to guanidines and 1,2-diamines, leading to pyrimidines and 1,4-diazepines, respectively.