3-tert-butylamino-2-nitro-2-propenal | 181294-58-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-tert-butylamino-2-nitro-2-propenal
• 英文别名: N-tert-butyl-β-formyl-β-nitroenamine；4-aza-5,5-dimethyl-2-nitro-2-hexenal；3-tert-butylamino-2-nitropropenal；3-(Tert-butylamino)-2-nitroprop-2-enal
• CAS: 181294-58-6
• 化学式: C₇H₁₂N₂O₃
• 分子量: 172.184
• InChiKey: DJIPEWIVRFHCOA-UHFFFAOYSA-N

物化性质

• 沸点：
  360.2±32.0 °C(Predicted)
• 密度：
  1.100±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  3-tert-butylamino-2-nitro-2-propenal 在 ammonium acetate 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以26%的产率得到2,6,9-triaza-4,8-dinitro[3.3.1]nona-3,7-diene
  参考文献：
  名称：

  N,N'-二烷基化2,6,9-三氮杂双环[3.3.1]壬二烯的合成及分子内环转化

  摘要：

  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。

  DOI：

  10.1039/d0ob01950j
• 作为产物：
  描述：

  tert-Butyl-{(E)-3-[(E)-tert-butylimino]-2-nitro-propenyl}-amine 在 silica gel 作用下， 反应 24.0h， 以98%的产率得到3-tert-butylamino-2-nitro-2-propenal
  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

• A Convenient Method for Synthesizing Modified 4-Nitrophenols
  作者：Yumi Nakaike、Yoshio Kamijo、Satoshi Mori、Mina Tamura、Nagatoshi Nishiwaki、Masahiro Ariga

  DOI：10.1021/jo0516990

  日期：2005.11.1

  β-Nitroenamine having a formyl group behaves as the synthetic equivalent of unstable nitromalonaldehyde upon treatment with ketones under basic conditions and leads to 2,6-disubstituted 4-nitrophenols. The present method is safer than the conventional one using sodium nitromalonaldehyde and enables the preparation of hitherto unknown nitrophenols.

  具有甲酰基的β-亚硝胺在碱性条件下用酮处理时表现为不稳定的亚硝基苯甲醛的合成当量，并导致2，6-二取代的4-硝基苯酚。本方法比使用次氮醛甲醛钠的常规方法更安全，并且能够制备迄今未知的硝基酚。
• 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。
• 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。
• Efficient synthesis of α-Nitro-β-Dialdimine ligands via Equilibrium–Controlling approach
  作者：Mahiro Nakabayashi、Nagatoshi Nishiwaki、Akitaka Ito、Shotaro Hayashi、Kento Iwai

  DOI：10.1016/j.tetlet.2022.153948

  日期：2022.7

  Reactions of β-formyl-β-nitroenamine with anilines afforded N,N’-diaryl-α-nitro-β-dialdimines; however, only small amounts of dialdimines were obtained when anilines possessing an electron-withdrawing group were employed. This disadvantage was overcome by adding anilinium salts to control the equilibrium, which resulted in the formation of dialdimines in considerably improved yields. This method facilitated

  β-甲酰基-β-硝基烯胺与苯胺反应得到N,N'-二芳基-α-硝基-β-二亚胺；然而，当使用具有吸电子基团的苯胺时，仅获得少量的二亚胺。通过添加苯胺盐来控制平衡来克服这一缺点，这导致二亚胺的形成以显着提高的产率。该方法有助于引入较少的亲核性 5-溴吡啶-2-基，这些基团有望成为各种框架的前体。制备的二亚胺作为配体形成具有扭曲四面体结构的镍(II)络合物。
• A New Approach to 6-Nitro-1H-[1,4]-diazepines
  作者：Masahiro Ariga、Nagatoshi Nishiwaki、Takuma Ogihara、Mina Tamura、Noriko Asaka、Kazushige Hori、Yasuo Tohda

  DOI：10.3987/com-02-9438

  日期：——