3,3-dimethyl-2-nitro-5-oxohexanenitrile | 70827-31-5

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 3,3-dimethyl-2-nitro-5-oxohexanenitrile
• 英文别名: 3,3-dimethyl-5-oxo-2-nitrohexanenitrile
• CAS: 70827-31-5
• 化学式: C₈H₁₂N₂O₃
• 分子量: 184.195
• InChiKey: PTNDNJSUBXDPEI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3-dimethyl-2-nitro-5-oxohexanenitrile 在 一水合肼 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以63%的产率得到3-amino-4,5-dihydro-4-nitro-5,5,7-trimethyl-6H-1,2-diazepine
  参考文献：
  名称：

  Ring construction via pseudo-intramolecular hydrazonation using bifunctional δ-keto nitrile

  摘要：

  An alpha-nitro-delta-keto nitrile efficiently reacted with hydrazines at room temperature, even in the absence of a catalyst, to afford the corresponding hydrazones; the reactions proceeded through a pseudo-intramolecular process. The hydrazone derived from hydrazine monohydrate underwent water-assisted cyclization, which yielded the corresponding diazepine. The hydrazones derived from 4-nitrophenylhydrazine and 2,4-dinitrophenylhydrazine were converted into pyridazines upon being heated in DMSO. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.10.159
• 作为产物：
  描述：

  丙酮 、 4-硝基-5(2)-异恶唑酮吡啶盐 在 四氢吡咯 作用下， 以 苯 为溶剂， 反应 2.5h， 以167 mg的产率得到3,3-dimethyl-2-nitro-5-oxohexanenitrile
  参考文献：
  名称：

  Pseudo-intramolecular Cyclization of α-Nitro-δ-keto Nitrile Leading to 2-Amino-3-nitro-1,4-dihydropyridines

  摘要：

  一种新概念--假分子内过程--被应用于多官能化杂环化合物的合成。酸性 α-硝基-δ-酮腈在与胺处理后很容易形成铵盐。当胺在平衡状态下释放出来时，亲核胺和亲电酮腈就形成了亲密的一对，从而使胺有效地攻击酮腈的氰基。随后的环化反应产生了部分结构的 1,4-二氢吡啶，其邻接位置含有一个氨基和一个硝基。

  DOI：

  10.1246/cl.2009.680

文献信息

• Bicyclization involving pseudo-intramolecular imination with diamines
  作者：Nagatoshi Nishiwaki、Shotaro Hirao、Jun Sawayama、Kazuhiko Saigo、Kazuya Kobiro

  DOI：10.1039/c1cc10705d

  日期：——

  α-Nitro-δ-keto nitriles and α-nitro-δ-keto ester were readily converted to diazabicyclo compounds having vicinal functionality upon treatment with diamines. The keto nitrile attracts the diamine nearby to an acidic hydrogen to cause the pseudo-intramolecular imination which proceeds efficiently without any catalyst at room temperature.

  α-硝基-δ-酮腈和α-硝基-δ-酮酯经二胺处理后很容易转化为具有邻接官能团的二氮杂双环化合物。酮腈吸引二胺附近的酸性氢，导致伪分子内亚氨基化，这种亚氨基化在室温下无需任何催化剂即可高效进行。
• Synthesis of vicinally functionalized 1,4-dihydropyridines and diazabicycles via a pseudo-intramolecular process
  作者：Nagatoshi Nishiwaki、Shotaro Hirao、Jun Sawayama、Haruyasu Asahara、Ryuichi Sugimoto、Kazuya Kobiro、Kazuhiko Saigo

  DOI：10.1016/j.tet.2013.11.044

  日期：2014.1

  An alpha-nitro-delta-keto nitrile readily forms the corresponding ammonium salt immediately upon treatment with an amine. When the amine liberated under equilibrium, the nucleophilic amine and the electrophilic keto nitrile come close to each other to afford so-called an intimate pair. The spatial proximity realized an efficient reaction to give a 2-amino-3-nitro-1,4-dihydropyridine; the reaction proceeded like an intramolecular reaction although it is actually an intermolecular reaction, namely the pseudo-intramolecular reaction. The bifunctionality of the keto nitrile also enabled the pseudo-intramolecular imination followed by tandem cyclization leading to diazabicyclic frameworks. (C) 2013 Elsevier Ltd. All rights reserved.
• A Simple Synthesis of a-Nitro-d-keto Nitrile
  作者：Nagatoshi Nishiwaki、Tomoko Nogami、Masahiro Ariga

  DOI：10.3987/com-07-11255

  日期：——

  alpha-Nitro-delta-keto nitrile was effectively synthesized in one-pot from pyridinium salt of nitroisoxazolone by ring opening reaction followed by condensation with two molecules of acetone via pyrrolidinium salt of 2,4-di-aci-nitropentanedinitrile. The obtained alpha-nitro-delta-keto nitrile has a highly acidic hydrogen in addition to multi-functionality. These structural features are considered to be useful for the syntheses of polyfunctionalized compounds.
• PECHENKO L. M.; POLYANSKAYA A. S.; PEREKALIN V. V.; ABOSKALOVA N. I.; DEM+, 31-E GERTSENOVSK. CHTENIYA. METODY SINTEZA, STROENIE I XIM. PREVRASHCHENI+
  作者：PECHENKO L. M.、 POLYANSKAYA A. S.、 PEREKALIN V. V.、 ABOSKALOVA N. I.、 DEM+

  DOI：——

  日期：——
• Pseudo-intramolecular Cyclization of α-Nitro-δ-keto Nitrile Leading to 2-Amino-3-nitro-1,4-dihydropyridines
  作者：Nagatoshi Nishiwaki、Kengo Kakutani、Mina Tamura、Masahiro Ariga

  DOI：10.1246/cl.2009.680

  日期：2009.7.5

  A novel concept—the pseudo-intramolecular process—is applied to the synthesis of multiply functionalized heterocyclic compounds. Acidic α-nitro-δ-keto nitrile easily forms an ammonium salt upon treatment with an amine. When the amine is liberated under equilibrium, an intimate pair, namely, a nucleophilic amine and an electrophilic keto nitrile are located close to each other, is formed; thus the amine efficiently attacks a cyano group of keto nitrile. As a result of subsequent cyclization, 1,4-dihydropyridines containing an amino and a nitro group at the vicinal positions as a partial structure are afforded.

  一种新概念--假分子内过程--被应用于多官能化杂环化合物的合成。酸性 α-硝基-δ-酮腈在与胺处理后很容易形成铵盐。当胺在平衡状态下释放出来时，亲核胺和亲电酮腈就形成了亲密的一对，从而使胺有效地攻击酮腈的氰基。随后的环化反应产生了部分结构的 1,4-二氢吡啶，其邻接位置含有一个氨基和一个硝基。